S1

Supporting Information for

Selective Incorporation of Primary Amines into a Tri-zirconium

Imido System and Catalytic Cyclization of Aminoalkynes

Masataka Oishi,‡* Yusuke Nakanishi,† and Hiroharu Suzuki† ‡School of Materials and Chemical Technology, Tokyo Institute of Technology, 2-12-1 O-okayama,

Meguro-ku, Tokyo 152-8552, Japan †Graduate School of Science and Engineering, Tokyo Institute

of Technology, 2-12-1 O-okayama, Meguro-ku, Tokyo 152-8552, Japan

INDEX

General procedures ··············································································································· S2

Instrumentation ··············································································································· S2

Figure S1 ·································································································································· S3

Synthesis of 2 ··············································································································· S4

NMR-scale reaction of 2 with n-PrNH2 ·········································································· S4

Figures S2-1 and S2-2 ··············································································································· S6

NMR-scale reaction of 2 with EtNH2 ·········································································· S7

NMR-scale reaction of 2 with i-BuNH2 ·········································································· S8

Reaction of 2 with neo-PenNH2 ····························································································· S8

Reaction of 2 with anilines ····························································································· S9

Figure S3 ·································································································································· S11

Synthesis of 7 ··············································································································· S12

Reaction of 8 with neo-PenNH2 ····························································································· S12

Figure S4 ·································································································································· S13

Figures S5 and S6 ··············································································································· S14

Figure S7 ·································································································································· S15

Figure S8 ·································································································································· S16

Thermolysis of 3 and 4 ··············································································································· S17

Figures S9 and S10 ··············································································································· S18

Synthesis of 13c and 14a ····························································································· S19

Catalytic cyclization of aminoalkynes 13 and 14 ······················································· S21

Figure S11 ·································································································································· S22

Stoichiometric reaction of 2 and 13c ·········································································· S22

Figure S12 ·································································································································· S23

Figure S13 ·································································································································· S24

Semi-catalytic reaction of 2 and 14b ·········································································· S25

Figure S14 ·································································································································· S25

Figure S15 ·································································································································· S26

Figure S16 ·································································································································· S27

Table S1 ································································································································ S28

NMR spectra ·············································································································· S31

S2

General Procedures. All manipulations for air- and moisture-sensitive compounds were carried out

under an argon atmosphere using standard Schlenk techniques or in a glovebox filled with argon or

nitrogen (H2O < 1 ppm, O2 < 1 ppm). Dehydrated solvents (tetrahydrofuran, toluene, pentane, ether)

were purchased from Kanto Chemical Co. Ltd. Deuterated solvents (benzene-d6, chloroform-d,

toluene-d8) were purchased from Cambridge Isotope Laboratories, Inc and Sigma-Aldrich Co.

Deuterated/non-deuterated hydrocarbon and ethereal solvents were distilled from Na-K alloy and

stored under an argon atmosphere. Commercially available organic substrates were purified by

distillation or sublimation. Other reagents and organic chemicals were used as received.

2-(2,3,4,5-Tetramethylcyclopentadienyl)ethanamine,1 Me2Si(η5-C5Me4)(Nt-Bu)Zr(NMe2)2 (8),2 and

aminoalkynes 13a, 13b, and 14b3 were prepared according to the literature procedures or the

modified ones.

Instrumentation. 1H and 13C NMR spectra were recorded on Varian INOVA 400 and Varian

400-MR Fourier transform spectrometers. 1H chemical shifts were referenced to the residual proton

peaks of benzene-d6 at δ 7.15 ppm, chloroform-d at δ 7.25 ppm, or toluene-d8 (meta-proton) at δ 7.09

ppm vs. tetramethylsilane. NMR yields were estimated by integration changes based on integrations

of bis(trimethylsilyl)methane as an internal standard. The central peaks of triplet for benzene-d6 at δ

128.1 ppm or chloroform-d at δ 77.2 ppm vs. tetramethylsilane were used as 13C NMR internal

references. Elemental analyses were recorded on a Perkin-Elmer 2400II. Single crystals suitable for

X-ray analysis were coated with Paratone-N in a glovebox. Crystals of proper size were picked by

using nylon CryoLoopTM and quickly transferred in a low temperature N2 stream to the goniometer

head. The diffraction data were collected on a R-AXIS RAPID diffractometer equipped with

graphite-monochromated Mo Kα radiation (λ = 0.71069 Å). Structures were solved by using

SHELXT and expanded using Fourier techniques. The non-hydrogen atoms were refined by

full-matrix least-square refinement in F2 using SHELXL 2014.4 Hydrogen atoms were located by

difference Fourier maps and refined isotropically. Crystal, measurement, refinement data for

complexes 2, 3a, 4a, 4c, 5, 6b, and 7 are summarized in Table S1.

1 Van Leusen, D.; Beetstra, D. J.; Hessen, B.; Teuben, J. H. Organometallics 2000, 19, 4084. 2 Carpenetti, D. W.; Kloppenburg, L.; Kupec, J. T.; Petersen, J. L. Organometallics 1996, 15, 1572. 3 (a) Li, Y.; Fu, P.-F.; Marks, T. J. Organometallics 1994, 13, 439. (b) McGrane, P. L.; Jensen, M.; Livinghouse, T. J. Am. Chem. Soc. 1992, 114, 5459. (c) Duncan, D.; Livinghouse, T. Organometallics 1999, 18, 4421. 4 G. M. Sheldrick, SHELXTL Version 2014/7. http://shelx.uni-ac.gwdg.de/SHELX/index.php.

S3

Figure S1. 1H NMR spectra of exo-olefinic isomer-major sample of 1 (top) and an isomeric mixture

of 1 after isomerization by HCl (bottom) (solvent: CDCl3). The asterisks denote solvent signals.

major*

*

S4

Synthesis of 2

(2,3,4,5-Tetramethylcyclopenta-1,4-dienyl)-1-ethanamine (1) (4.20 mmol, 0.70 g) was dissolved in

dry toluene (40 mL) under argon atmosphere. In a glovebox, Zr(NMe2)4 (4.20 mmol, 1.15 g) was

added to the solution at ambient temperature. After evacuated at –78 ºC, the mixture was heated at

60 ºC for 40 h. Then, all volativels were removed under reduced pressure and the residue was

washed with pentane and dried in vacuo to afford 2 as a light yellow powder (0.67 g, 54%). Crystals

suitable for X-ray analysis was obtained from toluene at –30 ºC. Note that the corresponding

reaction with the exo-olefin isomer of 1 [i.e., 2-(2,3,4,5-tetramethyl-2-cyclopenten-1-

ylidene)ethanamine] does not produce complex 2. The following NMR assignments for 2 were made

by COSY, HMQC, and HMBC experiments.

[(LZrNMe2)3] (2) (L = η5-C5Me4CH2CH2N): 1H NMR (C6D6, 400 MHz): δ 4.71 (1H, ddd, J = 6.4,

10.8, 13.5 Hz, NCHHCH2), 4.60 (1H, ddd, J = 6.4, 10.5, 13.4 Hz, N′CHHCH2), 4.22 (1H, ddd, J =

5.8, 10.1, 12.4 Hz, N″CHHCH2), 3.92 (1H, ddd, J = 2.3, 5.6, 12.4 Hz, N″CHHCH2), 3.60 (1H, dd, J

= 5.8, 13.5 Hz, NCHHCH2), 3.47 (1H, dd, J = 5.8, 13.4 Hz, N′CHHCH2), 2.97 (6H, s, NMe2), 2.95

(6H, s, NMe2), 2.76 (6H, s, NMe2), 2.77–2.70 (1H, overlap, NCH2CHH), 2.76–2.67 (1H, overlap,

N′CH2CHH), 2.74–2.67 (1H, overlap, NCH2CHH), 2.72–2.65 (1H, overlap, N′CH2CHH), 2.67–2.60

(1H, overlap, N″CH2CHH), 2.65–2.59 (1H, overlap, N″CH2CHH), 2.12, 2.100, 2.096, 2.05, 2.05,

2.01, 1.98, 1.98, 1.96, 1.94, 1.92, 1.91 (3H × 12, s, C5Me4 × 3) ppm. 13C{1H} NMR (C6D6, 100

MHz): δ 130.3, 130.0, 125.9, 120.9, 119.6, 118.7, 118.6, 118.3, 117.8, 116.6, 116.0, 115.0, 114.2,

113.7, 113.5 (C5Me4 × 3), 60.7 (NCH2CH2), 59.7 (N′CH2CH2), 58.5 (N″CH2CH2), 46.7 (NMe2),

46.1 (NMe2), 44.8 (NMe2), 29.5 (N″CH2CH2), 28.7 (NCH2CH2), 28.3 (N′CH2CH2), 12.9, 11.7, 11.60,

11.58, 11.1, 10.9, 10.9, 10.8, 10.73, 10.69, 10.63, 10.55 (C5Me4 × 3) ppm. Anal. Calcd for

C39H66N6Zr3: C, 52.47; H, 7.45; N, 9.41. Found: C, 52.70; H, 7.39; N, 9.50.

NMR-scale reaction of 2 with n-PrNH2

(i) Reaction monitoring at 25 °C

In the glovebox, complex 2 (6.3 μmol, 5.6 mg) was dissolved in C6D6 (0.4 mL) with the internal

standard (Me3Si)2CH2. An NMR spectrum was recorded before addition of n-PrNH2. A solution of

n-PrNH2 (1.1 M in C6D6, 57 μmol, 52 μL) was then added at 25 °C. The reaction was monitored by 1H NMR analysis. About 4 equiv of n-PrNH2 was reacted with 2 in 15 min, producing almost a

single product 3akinetic. However, the product gradually disappeared and, after 16 h, was mostly

replaced by a thermodynamically stable structure 3a with no change of intensity of free n-PrNH2.

The yield of 3a at t = 16 h was estimated by 1H NMR analysis to be 92%. NMR data of 3akinetic and

3a are given below, and the 1H NMR comparison is shown in Figure S2-1 and S2-2.

3akinetic: Partial 1H NMR (C6D6, 400 MHz): δ 4.85–4.73 (2H, m), 4.48 (1H, dd, J = 4.0, 12.0 Hz),

4.03–3.92 (1H, m), 3.65–3.43 (2H, m), 3.41–3.14 (4H, m), 3.12–2.98 (2H, m), 2.91–2.69 (3H, m),

S5

2.65–2.52 (2H, m), 2.52–2.43 (1H, m), 2.34–2.25 (3H, m), 2.23, 2.20, 2.17, 2.17, 2.14, 2.11, 1.997,

1.991, 1.97, 1.92 (3H × 12, s, C5Me4 × 3), 2.00–1.77 (2H, m), 1.63–1.34 (6H, m), 1.06–0.98 (10H, m,

μ-NCH2CH2CH3 × 3 and other), 0.93 (3H, t, J = 7.4 Hz, NHCH2CH2CH3), 0.82–0.71 (1H, m), 0.29

(1H, br d, J = 6.4 Hz) ppm.

[(LZrNHPr)(LHZrNHPr)(LHZr)(μ-NHPr)(μ3-NPr)] (3a): 1H NMR (C6D6, 400 MHz): δ

4.54–4.46 (1H, overlap, NCHHCH2C5Me4), 4.53–4.44 (1H, overlap, HN1CH2CH2CH3), 4.38 (1H,

dd, J = 4.9, 11.8 Hz, HN2CH2CH2CH3), 4.09 (1H, dt-like ddd, J = 2.6, 13.2 Hz, N3CHHCH2CH3),

3.97 (1H, dt-like ddd, J = 2.0, 12.8 Hz, HN′CHHCH2C5Me4), 3.82 (1H, dt-like ddd, J = 5.9, 12.4 Hz,

N3CHHCH2CH3), 3.70 (1H, m, HN2CHHCH2CH3), 3.66–3.53 (1H, overlap, HN″CHHCH2C5Me4),

3.66–3.52 (1H, overlap, NCHHCH2C5Me4), 3.60–3.50 (1H, overlap, HN′CHHCH2C5Me4),

3.56–3.41 (2H, overlap, HN1CH2CH2CH3), 3.45–3.35 (1H, overlap, HN″CHHCH2C5Me4), 3.31 (1H,

m, HN2CHHCH2CH3), 2.84 (2H, m, HN4CH2CH2CH3), 2.63–2.52 (2H, overlap, NCH2CH2C5Me4),

2.50–2.34 (2H, overlap, HN′CH2CH2C5Me4), 2.48–2.36 (1H, overlap, HN″CH2CHHC5Me4),

2.36–2.28 (1H, overlap, HN″CH2CHHC5Me4), 2.27, 2.20, 2.19, 2.18, 2.17, 2.15, 2.14, 2.01, 2.01,

1.95, 1.91, 1.88 (3H × 12, s, C5Me4 × 3), 1.71 (1H, m, HN4CH2CHHCH3), 1.63–1.50 (1H, overlap,

N3CH2CHHCH3), 1.56–1.45 (2H, overlap, HN2CH2CH2CH3), 1.55–1.42 (2H, overlap,

HN1CH2CH2CH3), 1.38 (1H, m, HN4CH2CHHCH3), 1.06 (3H, t, J = 7.4 Hz, HN2CH2CH2CH3), 1.01

(3H, t, J = 7.2 Hz, HN1CH2CH2CH3), 1.01–0.98 (1H, overlap, N3CH2CHHCH3), 0.95 (3H, t, J = 6.7

Hz, N3CH2CH2CH3), 0.93 (3H, t, J = 7.3 Hz, HN4CH2CH2CH3), 0.88–0.74 (1H, overlap,

HN″CH2CH2C5Me4), 0.82–0.72 (1H, overlap, HN′CH2CH2C5Me4), 0.37 (1H, dd, J = 5.1, 9.0 Hz,

HN4CH2CH2CH3) ppm. 13C{1H} NMR (C6D6, 100 MHz): δ 129.6, 128.6, 122.3, 122.1, 118.3, 118.0,

117.6, 117.5, 116.6, 116.4, 116.1, 115.2, 115.0, 114.4, 113.8 (C5Me4 × 3), 63.0 (NCH2), 60.1

(HN′CH2), 55.7 (HN″CH2), 59.7 (N3CH2), 55.9 (HN4CH2), 54.7 (HN2CH2), 54.4 (HN1CH2), 31.5,

31.3, 28.9 (NCH2CH2C5Me4 × 3), 30.7 (N3CH2CH2), 30.4 (HN4CH2CH2), 30.0 (HN2CH2CH2), 29.5

(HN1CH2CH2), 13.4, 13.2, 13.1, 12.4, 12.2, 12.1, 11.9, 11.54, 11.47, 11.43, 11.38, 10.6 (C5Me4 × 3),

12.9 (N3CH2CH2CH3), 12.7 (HN4CH2CH2CH3), 12.3 (HN1CH2CH2CH3), 11.6 (HN2CH2CH2CH3)

ppm. Single crystals of 3a were obtained from a concentrated toluene solution at 25 °C and the

structure was determined by XRD analysis.

(ii) Formation of 4a

In the glovebox, 2 (22 μmol, 20 mg) was dissolved in toluene (0.8 mL) in a Teflon-valved Schlenk

tube. Out of the box, n-PrNH2 (97 μmol, 8 μL) was then added under argon purge. After 3 h at 25 °C,

Volatiles were removed under reduced pressure, giving a mixture of 3a and 4a as a waxy oil (20 mg,

combined yield: 95%). The 1H NMR pattern of 4a in the 4a-major sample was compared with that of

3a (containing n-PrNH2) and i-BuNH2-derived 4c. The ratio of 3a and 4a was estimated by integral

values of separated signals of the methyl groups of C5Me4 (δ = 1.91 ppm for 3a and 1.80 ppm for

4a) to be 39:61. Crystals of 4a were eventually obtained from the 4a-major sample and the structure

S6

of 4a was determined by preliminary XRD analysis and its comparison with that of 4c.

Figure S2-1. 1H NMR spectra of the NMR-scale reaction of 2 and n-PrNH2 (C6D6, 25 °C).

Figure S2-2. Partial 1H NMR spectra of the NMR-scale reaction of 2 and n-PrNH2 (C6D6, 25 °C).

ppm (f1)0.01.02.03.04.05.0

≈≈

≈≈

t = 15 min

t = 16 h

(Me3Si)2CH2 (internal standard)f ree n-PrNH2

ppm (f1)1.701.801.902.002.102.202.30

Me2NH

Me2NH

C5Me4 and NCH2CH2CH3 of 3akineticC5Me4 and NCH2CH2CH3 of 3at= 15 min

t= 16 h

1.00 0.901.10

3H9H

6H3H 3H

S7

[(LZrNHPr-n)2(LHZr)(μ-NPr-n)] (4a): Partial 1H NMR (C6D6, 400 MHz): δ 4.97 (1H, dd,

NCHHCH2C5Me4), 4.88 (1H, ddd, NCHHCH2C5Me4), 4.49 (2H, m, N′CH2CH2C5Me4), 3.92 (1H,

dt-like ddd, J = 4.2, 11.2 Hz), 3.62 (2H, m), 3.56−3.37 (4H, m, N″CHHCH2C5Me4 + others),

3.37−3.25 (2H, m), 3.05 (1H, td-like ddd, J = 5.6, 13.2 Hz, N″CHHCH2C5Me4), 2.85 (1H, ddd, J =

7.6, 10.8, 12.4 Hz, NCH2CHHC5Me4), 2.78−2.69 (2H, m, NCH2CHHC5Me4 + N′CH2CHHC5Me4),

2.52 (1H, td-like ddd, J = 7.2, 12.8 Hz), 2.39 (2H, m), 2.26, 2.18, 2.18, 2.13, 2.13, 2.12, 2.08, 2.06,

2.03, 1.93, 1.80, 1.71 (3H × 12, s, C5Me4 × 3), 1.59 (2H, m), 1.53–1.38 (2H, m), 1.35 (1H, dd, J =

5.6, 14.0 Hz), 1.09 (3H, t, μ-NCH2CH2CH3), 0.99 (3H × 2, t, NHCH2CH2CH3) ppm.

NMR-scale reaction of 2 with EtNH2

Similarly to the formation of 3a, a NMR-scale reaction of 2 with an excess amount of EtNH2 was

examined. In the box, complex 2 (6.2 μmol, 5.5 mg) and internal standard were dissolved in C6D6

(0.5 mL). After a 1H NMR spectrum was recorded, a THF solution of EtNH2 (2.0 M, 25 μL) was

syringed in at 25 °C. The reaction was monitored by NMR spectroscopy. Singlet signals for C5Me4

groups of 3bkinetic were observed as the major product at t = 20 min. After 21 h, majority of these

signals were replaced by those of 3b: 3bkinetic, 15% NMR yield; 3b, 65% NMR yield. Neither 3bkinetic

nor 3b were isolated and thermodynamically stable 3b was identified by comparison of the

following 1H NMR data with those of 3a.

3bkinetic: Partial 1H NMR (C6D6, 400 MHz): δ 2.17, 2.17, 2.15, 2.14, 2.13, 2.08, 1.99, 1.98, 1.96, 1.94,

1.90, 1.90 (3H × 12, s, C5Me4 × 3) ppm.

[(LZrNHEt)(LHZrNHEt)(LHZr)(μ-NHEt)(μ3-NEt)] (3b): 1H NMR (C6D6, 400 MHz): δ 4.49 (1H,

dd, J = 5.8, 12.6 Hz, NCHHCH2C5Me4), 4.39 (1H, dd, J = 5.4, 11.0 Hz, HN1CH2CH3), 4.33–4.20

(1H, overlap, N3CHHCH3), 4.29 (1H, overlap, HN2CH2CH3), 3.96 (1H, dd, J = 6.2, 13.0 Hz,

HN′CHHCH2C5Me4), 3.90–3.78 (1H, m, N3CHHCH3), 3.80–3.67 (1H, m, HN1CHHCH3), 3.66–3.50

(1H, overlap, HN″CHHCH2C5Me4), 3.65–3.53 (1H, overlap, NCHHCH2C5Me4), 3.60–3.48 (2H,

overlap, HN2CH2CH3), 3.59–3.50 (1H, overlap, HN′CHHCH2C5Me4), 3.46–3.36 (1H, overlap,

HN″CHHCH2C5Me4), 3.44–3.30 (1H, m, HN1CHHCH3), 3.03 (2H, m-like qd, J = 6.9, Hz,

HN4CH2CH3), 2.56 (1H, m, NCH2CHHC5Me4), 2.49–2.38 (1H, overlap, HN″CH2CHHC5Me4),

2.48–2.34 (2H, overlap, HN′CH2CH2C5Me4), 2.42–2.34 (1H, overlap, HN″CH2CHHC5Me4), 2.30

(1H, m, NCH2CHHC5Me4), 2.24, 2.17, 2.160, 2.156, 2.14, 2.13, 2.12, 2.004, 1.996, 1.93, 1.88, 1.87

(3H × 12, s, C5Me4 × 3), 1.20 (3H, t, J = 7.2 Hz, HN4CH2CH3), 1.16 (3H, t, J = 7.0 Hz,

HN1CH2CH3), 1.15 (3H, t, J = 7.0 Hz, HN2CH2CH3), 1.13 (3H, t, J = 7.0 Hz, N3CH2CH3), 0.89–0.78

(1H, overlap, HN″CH2CH2C5Me4), 0.84–0.74 (1H, overlap, HN′CH2CH2C5Me4), 0.22 (1H, t, J = 6.7

Hz, HN4CH2CH3) ppm.

S8

NMR-scale reaction of 2 with i-BuNH2

In the glovebox, 2 (11 μmol, 10.0 mg) was dissolved in C6D6 (0.4 mL) with the internal standard in a

Teflon-valved NMR tube. i-BuNH2 (55 μmol, 5.5 μL) was added after a 1H NMR spectrum was

recorded. The reaction progress was monitored by NMR spectroscopy. After 12 h, complex 4c was

yielded quantitatively. The structure was determined by NMR and X-ray analysis.

[(LZrNHBu-i)2(LHZr)(μ-NBu-i)] (4c): 1H NMR (C6D6, 400 MHz): δ 4.98 (1H, dd, J = 6.8, 11.4

Hz, NCHHCH2), 4.86 (1H, dt-like ddd, J = 6.8, 11.4 Hz, NCHHCH2), 4.60–4.48 (2H, m,

N′CH2CH2), 3.74 (1H, dd, J = 5.8, 13.0 Hz, N3CHHCHMe2), 3.67 (1H, t-like dd, J = 7.4 Hz,

HN1CH2CHMe2), 3.50 (1H, t-like dd, J = 7.6 Hz, HN2CH2CHMe2), 3.45–3.22 (1H, overlap,

HN1CHHCHMe2), 3.40 (1H, dt-like ddd, J = 4.8, 13.2 Hz, HN″CHHCH2), 3.35–3.25 (1H, overlap,

N3CHHCHMe2), 3.38–3.19 (2H, overlap, HN2CH2CHMe2), 3.13 (1H, td-like ddd, J = 7.4, 12.4 Hz,

HN1CHHCHMe2), 3.03 (1H, td-like ddd, J = 6.0, 13.2 Hz, HN″CHHCH2), 2.85 (1H, m, NCH2CHH),

2.77–2.67 (1H, overlap, N′CH2CHH), 2.75–2.66 (1H, overlap, NCH2CHH), 2.51 (1H, dt-like ddd, J

= 5.6, 12.8 Hz, N′CH2CHH), 2.38 (1H, J = 4.4, 14.0 Hz, HN″CH2CHH), 2.28–2.12 (1H, overlap,

HN″CH2CHH), 2.27, 2.20, 2.18, 2.17, 2.143, 2.12, 2.07, 2.06, 2.03, 1.93, 1.82, 1.69 (3H × 12, s,

C5Me4 × 3), 1.81–1.68 (1H, overlap, N3CH2CHMe2), 1.73–1.60 (1H, overlap, HN2CH2CHMe2), 1.52

(1H, m, HN1CH2CHMe2), 1.40 (1H, dd, J = 6.0, 13.2 Hz, HN″CH2CH2), 1.099 (3H, d, J = 6.4 Hz,

HN2CH2CHMeMe), 1.096 (3H, d, J = 6.8 Hz, HN2CH2CHMeMe), 1.02 (3H, d, J = 6.4 Hz,

HN1CH2CHMeMe), 1.01 (3H, d, J = 6.4 Hz, HN1CH2CHMeMe), 0.95 (3H, d, J = 6.4 Hz,

N3CH2CHMeMe), 0.91 (3H, d, J = 6.4 Hz, N3CH2CHMeMe) ppm. 13C{1H} NMR (C6D6, 100 MHz):

δ 133.7, 125.2, 124.2, 119.5, 119.4, 117.9, 117.0, 116.42, 116.37, 115.6, 115.0, 114.9, 114.7, 114.0,

112.8 (C5Me4 × 3), 72.0 (NCH2CH2), 66.5 (N3CH2CHMe2), 65.7 (N′CH2CH2), 60.6

(HN1CH2CHMe2), 59.3 (HN2CH2CHMe2), 55.9 (HN″CH2CH2), 34.3 (HN1CH2CHMe2), 34.1

(N3CH2CHMe2), 33.8 (HN2CH2CHMe2), 32.1 (N′CH2CH2), 29.3 (NCH2CH2), 29.1 (HN″CH2CH2),

21.5, 21.1, 21.1, 21.0. 21.0, 20.8 (NCH2CHMe2 × 3), 12.1, 12.0, 11.8, 11.76, 11.74, 11.68, 11.6, 11.5,

11.2, 10.93, 10.88, 10.5 (C5Me4 × 3) ppm.

Reaction of 2 with neo-PenNH2

In the glovebox, 2 (0.054 mmol, 48 mg) was dissolved in toluene (8.0 mL). Outside of the box,

neo-PenNH2 (0.33 mmol, 39 μL) was then added to the solution under an argon purge. The mixture

was stirred at ambient temperature for 10 min. Removal of all volatiles gave crude 5, which was

washed with pentane and dried in vacuo, affording a light yellow powder (47 mg, quant).

[(LZr)2(LZrNMe2)(μ-NPen-neo)] (5): 1H NMR (C6D6, 400 MHz): δ 5.15–5.02 (1H, overlap,

NCHHCH2), 5.14–5.03 (1H, overlap, N′CHHCH2), 4.94 (1H, dd, J = 6.6, 12.6, NCHHCH2), 4.80

(2H, m, N″CH2CH2), 4.40 (1H, dd, J = 7.2, 12.6, N′CHHCH2), 2.94 (1H, ddd, J = 7.2, 11.5, 13.5 Hz,

NCH2CHH), 2.86–2.72 (1H, overlap, NCH2CHH), 2.85–2.64 (1H, overlap, N′CH2CHH), 2.84–2.65

S9

(2H, overlap, N″CH2CH2), 2.81 (6H, s, NMe2), 2.45 (1H, ddd, J = 7.7, 11.5, 13.3 Hz, N′CH2CHH),

2.24–2.19 (1H, overlap, NCHHCMe3), 2.24, 2.23, 2.19, 2.17, 2.16, 2.10, 2.03, 2.02, 1.98, 1.92, 1.91,

1.87 (3H × 12, s, C5Me4 × 3), 1.51 (1H, d, J = 12.4 Hz, NCHHCMe3), 0.85 (9H, s, CMe3) ppm. 13C{1H} NMR (C6D6, 100 MHz): δ 132.4, 130.2, 128.8, 122.6, 121.2, 120.8, 119.8, 118.6, 116.3,

115.3, 114.9, 114.0, 113.9, 113.9, 113.4 (C5Me4 × 3), 70.5 (N″CH2CH2), 67.7 (NCH2CH2), 63.7

(N′CH2CH2), 62.4 (NCH2CMe3), 45.2 (NMe2), 33.8 (CMe3), 31.2 (N′CH2CH2), 30.1 (NCH2CH2),

29.4 (N″CH2CH2), 28.3 (CMe3), 12.7, 12.3, 11.8, 11.7, 11.31, 11.27, 10.16, 10.13, 11.0, 10.89, 10.88,

10.5 (C5Me4 × 3) ppm. Anal. Calcd for C40H65N5Zr3: C, 54.00; H, 7.36; N, 7.87. Found: C, 53.75; H,

7.68; N, 7.72.

Reaction of 2 with anilines

[(LZr)(LZrNHPh)(LH2Zr)(μ-NPh)2] (6a): In the glovebox, 2 (0.014 mmol, 13.0 mg) was

dissolved in C6D6 (0.4 mL) with the internal standard. After 1H NMR spectrum was recorded, aniline

(0.049 mmol, 4.5 μL) was added under argon into the NMR tube. The reaction progress was

monitored at 25 ºC by 1H NMR analysis. After 19h, 6a was formed in 77% yield. The structure was

identified by comparison of the following partial NMR data with those of fully characterized 6b. 1H NMR (C6D6, 400 MHz): δ 7.41–7.18 (4H, m, ArH), 7.03–6.72 (7H, m, ArH), 6.62–6.50 (4H, m,

ArH), 5.43 (1H, m, NCHHCH2), 5.40 (1H, s, NHZr), 4.60 (1H, ddd, J = 2.2, 8.1, 14.7 Hz,

NCHHCH2), 4.10 (1H, dd, J = 5.1, 5.5 Hz, N′CHHCH2), 3.41 (1H, m, N′CH2CHH), 2.85 (1H, m,

N′CH2CHH), 2.79 (1H, m, NCH2CHH), 2.67 (1H, ddd, J = 2.2, 7.3, 13.7 Hz, NCH2CHH), 2.37 (1H,

m, N′CHHCH2), 2.00 (1H, m, N″HH), 2.43, 2.30, 2.16, 2.04, 1.95, 1.914, 1.910, 1.86, 1.82, 1.79,

1.78, 1.52 (3H × 12, s, C5Me4 × 3), 1.75–1.55 (3H, m, N″CHHCH2), 1.36 (1H, m, N″CHHCH2),

0.78 (1H, m, N″HH) ppm. 13C NMR (C6D6, 100 MHz): δ 160.4, 159.1, 156.0, 129.7, 134.7, 125.6,

125.3, 123.9, 122.7, 121.6, 121.3, 120.9, 120.7, 120.4, 119.3, 119.2, 118.6, 118.2, 118.1, 118.0,

117.74, 117.70, 117.3, 116.0, 115.7, 115.6, 115.0, 113.5, 111.8 (Ar and C5Me4), 71.7, 51.3, 44.3

(NCH2CH2 × 3), 30.3, 28.5, 24.1 (NCH2CH2 × 3), 14.6, 13.3, 12.5, 12.2, 11.804, 11.796, 11.6, 11.1,

11.0, 10.8, 10.1, 9.8 (C5Me4 × 3) ppm.

[(LZr){LZr(NHC6H4-4-Br)}(LH2Zr)(μ-NC6H4-4-Br)2] (6b): In the glovebox, 2 (0.011 mmol, 9.5

mg) was dissolved in C6D6 (0.5 mL) with the internal standard. After 1H NMR spectrum was

recorded, 4-bromoaniline (0.045 mmol, 7.8 mg, 4.3 equiv) was added into the NMR tube in the box.

The reaction progress was monitored at 25 ºC by 1H NMR analysis. After 72 h, 6b was formed in

87% yield. Complex 6b was also synthesized in a preparative scale since isolation of crystalline 6b

was successful. In the glovebox, 2 (0.0735 mmol, 65.6 mg) was dissolved in toluene (10 mL) with

p-bromoaniline (0.445 mmol, 76.5 mg, 6 equiv) at ambient temperature. This solution was heated at

60 °C. After heating for 24 h, the solution was cooled to room temperature and all volatiles were

removed under reduced pressure. In the box, the residue was washed with pentane and dried to give

the desired 6b (71.3 mg, 76% yield). 6b was recrystallized from toluene at −30°C.

S10

1H NMR (C6D6, 400 MHz): δ 7.47 (1H, br, ArH), 7.35 (2H + 1H, overlap, Ar′H, ortho and ArH),

6.98 (2H, d, J = 8.8 Hz, Ar″H, ortho), 6.82 (1H, br, ArH), 6.44 (2H, d, J = 8.8 Hz, Ar′H, meta), 6.27

(1H, br, ArH), 6.18 (2H, d, J = 8.8 Hz, Ar″H, meta), 5.14 (1H, m, NCHHCH2), 5.10 (1H, s, Ar′NH),

4.45 (1H, m, NCHHCH2), 4.00 (1H, m, N′CHHCH2), 3.34 (1H, m, N′CH2CHH), 2.79 (1H, m,

N′CH2CHH), 2.71 (1H, m, NCH2CHH), 2.56 (1H, m, NCH2CHH), 2.19 (1H, overlap, N′CHHCH2),

2.28, 2.22, 2.09, 1.95, 1.84, 1.79, 1.73, 1.72, 1.684, 1.681, 1.58, 1.40 (3H × 12, s, C5Me4 × 3), 1.73

(1H, overlap, N″HH), 1.62 (1H, m, N″CH2CHH), 1.53 (1H, overlap, N″CH2CHH), 1.51 (1H,

overlap, N″CHHCH2), 1.23 (1H, m, N″CHHCH2), 0.52 (1H, m, N″HH) ppm. 13C{1H} NMR (C6D6,

100 MHz): δ 159.2 (Ar″, ipso), 158.1 (Ar, ipso), 154.7 (Ar′, ipso), 131.7 (Ar, ortho), 131.5 (Ar′,

ortho), 131.1 (Ar″, ortho), 130.9 (Ar, ortho), 126.2 (Ar, meta), 126.1 (Ar, meta), 122.1 (Ar″, meta),

120.6 (Ar′, meta), 110.2 (Ar, para), 110.1 (Ar″, para), 106.9 (Ar′, para), 135.1, 126.0, 123.1, 121.9,

120.8, 120.5, 120.2, 119.6, 118.79, 118.78, 117.9, 116.0, 115.8, 113.8, 112.1 (C5Me4 × 3), 71.5

(NCH2CH2), 51.3 (N′CH2CH2), 44.4 (N″CH2CH2), 30.1 (NCH2CH2), 28.2 (N′CH2CH2), 23.9

(N″CH2CH2), 14.4, 13.3, 12.4, 12.0, 11.8, 11.7, 11.5, 10.9, 10.84, 10.76, 10.0, 9.8 (C5Me4 × 3) ppm.

Anal. Calcd for (C51H63Br3N6Zr3)(C7H8): C, 51.01; H, 5.24; N, 6.15. Found: C, 50.73; H, 5.16; N,

6.23.

[(LZr){LZr(NHC6H4-4-OMe)}(LH2Zr)(μ-NC6H4-4-OMe)2] (6c): In the glovebox, 2 (0.011 mmol,

10.0 mg) was dissolved in C6D6 (0.4 mL) with the internal standard. After 1H NMR spectrum was

recorded, p-anisidine (0.055 mmol, 6.8 mg) was added into the NMR tube in the box. The reaction

progress was monitored at 25 ºC by 1H NMR analysis. After 24h, 6c was formed in 84% yield. The

structure was identified by comparison of the following NMR data with those of fully characterized

6b. 1H NMR (C6D6, 400 MHz): δ 7.24 (1H, d, J = 8.0 Hz, ArH), 7.10 (1H, d, J = 8.0 Hz, ArH), 7.00

(2H, d, J = 8.8 Hz, ArH, ortho), 6.91 (1H, d, J = 8.4 Hz,ArH), 6.79 (2H, d, J = 8.8 Hz, ArH, ortho),

6.59 (2H, d, J = 8.8 Hz, ArH, meta), 6.54 (1H, d, J = 8.4 Hz, ArH), 6.49 (2H, d, J = 8.8 Hz, ArH,

meta), 5.42 (1H, ddd, J = 7.2, 7.4, 14.6 Hz, NCHHCH2), 5.37 (1H, s, ArNHZr), 4.68 (1H, ddd, J =

2.2, 5.7, 14.6 Hz, NCHHCH2), 4.14 (1H, ddd, J = 1.4, 6.1, 10.6 Hz, N′CHHCH2), 3.53 (3H, s,

ArOMe), 3.46 (3H, s, ArOMe), 3.41 (1H, m, N′CH2CHH), 3.32 (3H, s, ArOMe), 2.79 (1H, m,

N′CH2CHH), 2.78 (1H, m, NCH2CHH), 2.72 (1H, ddd, J = 2.2, 7.2, 13.7 Hz, NCH2CHH), 2.46 (1H,

m, N′CHHCH2), 2.02 (1H, m, N″HH), 2.44, 2.32, 2.18, 2.06, 1.98, 1.97, 1.94, 1.89, 1.85, 1.83, 1.81,

1.56 (3H × 12, s, C5Me4 × 3), 1.75–1.44 (4H, m, N″CH2CH2), 0.89 (1H, m, N″HH) ppm. 13C{1H}

NMR (C6D6, 100 MHz): δ 154.6, 152.6, 152.54, 152.52, 151.4, 150.2, 134.3, 125.3, 125.2, 124.1,

122.7, 121.4, 120.9, 120.10, 120.05, 119.9, 119.6, 118.9, 118.3, 117.8, 117.6, 115.7, 115.6, 115.3,

114.4, 111.6, 113.8, 113.6, 113.1 (Ar and C5Me5), 71.8 (NCH2), 55.4, 55.2, 55.0 (OMe × 3), 51.2

(N′CH2), 44.3 (N″CH2), 30.0 (NCH2CH2), 28.5 (N′CH2CH2), 24.1 (N″CH2CH2), 14.5, 13.2, 12.5,

12.1, 11.8, 11.7, 11.6, 11.1, 11.0, 10.9, 10.1, 9.8 (C5Me4 × 3) ppm.

S11

Figure S3. VT NMR spectra of 6b in toluene-d8 (aromatic region only). Solid circles

and open squares indicate Ar-H and Ar′-H (bridging imide ligands), respectively, and

solid triangles shows Ar″-H (terminal amide ligand). The asterisks denote solvent

signals.

373K

353K

333K

313K

273K

253K

233K

213K

**

*

* **

* **

* **

* **

**

*

**

*

* *

*

Zr N

Zr

N Zr

N

N

NH

Br

Br

Br

NH2

Ar

Ar

Ar

S12

Synthesis of 7

To a solution of complex 2 (5.5 mg, 6.2 μmol) in C6D6 (0.5 mL) with the internal standard was

added 2,6-di-tert-butylphenol (2 mg, 9.7 μmol) at 25 ºC. The solution color turned from yellow to

light yellow while the reaction proceeded gradually. After 24 h, 1H NMR analysis showed that

complex 7 was formed quantitatively. The reaction was either carried out in toluene, and 7 was

recrystallized from toluene-pentane. The structure was determined by NMR and XRD analysis, and

the following NMR assignment was made by COSY, HMQC, and HMBC experiments.

[(LZrNMe2)2(LZrOC6H3-2,6-t-Bu2)] (7): 1H NMR (C6D6, 400 MHz): δ 7.32 (1H, dd, J = 1.6, 7.6

Hz, ArH), 7.27 (1H, dd, J = 1.6, 7.6 Hz, ArH), 6.81 (1H, t, J = 7.6 Hz, ArH), 5.03 (1H, dt, J = 5.8,

12.0 Hz, NCHHCH2), 4.97–4.87 (2H, m, N′CHHCH2 and N″CHHCH2), 4.67 (1H, dd, J = 7.4, 12.4

Hz, N′CHHCH2), 4.61 (1H, td, J = 4.0, 12.4 Hz, N″CHHCH2), 4.41 (1H, dd, J = 7.6, 12.0 Hz,

NCHHCH2), 3.07 (6H, s, NMe2), 2.94 (1H, ddd, 7.6, 12.0, 13.2 NCH2CHH), 2.83 (1H, ddd, J = 7.4,

12.0, 13.4 Hz, N′CH2CHH), 2.68 (6H, s, NMe2), 2.64 (1H, dd, J = 5.6, 13.4 Hz, N′CH2CHH), 2.58

(2H, m, N″CH2CH2), 2.51 (1H, dd, J = 5.8, 13.2 Hz, NCH2CHH), 2.31, 2.26, 2.24, 2.05, 1.97, 1.97,

1.97, 1.94, 1.93, 1.93, 1.87, 1.81 (3H × 4 × 3, s, C5Me4), 1.64 (9H, s, t-Bu), 1.53 (9H, s, t-Bu) ppm. 13C{1H} NMR (C6D6, 100 MHz): δ 163.1 (OAr-1), 138.2, 136.9 (OAr-2,6), 128.5, 125.1 (OAr-3,5),

117.8 (OAr-4), 130.0, 128.1, 127.7, 125.5, 124.4, 122.0, 121.6, 121.3, 119.6, 119.4, 116.3, 116.2,

115.7, 115.7, 115.3 (C5Me4 × 3), 67.3, 67.0, 61.0 (NCH2 × 3), 50.3 (NMe2), 49.6 (NMe2), 37.1

(CMe3), 35.81 (CMe3), 35.78 (CMe3), 32.4 (CMe3), 29.8, 29.7, 29.4 (NCH2CH2 × 3), 14.3, 13.8,

12.9, 12.7, 12.2, 12.0, 11.9, 11.7, 11.6, 11.2, 10.5, 10.0 (C5Me4 × 3) ppm.

Reaction of 8 with neo-PenNH2

{Me2Si(C5Me4)(Nt-Bu)}Zr(NMe2)2 (8) (30 μmol, 13 mg) was dissolved in C6D6 (0.4 mL) with

(Me3Si)2CH2 as an internal standard. A solution of neo-PenNH2 in C6D6 (1.2 M, 70 μL) was added at

25 °C. The reaction in the sealed NMR tube was monitored by 1H NMR analysis. The reaction

reached the equilibrium in 5 h. The conversion of 8 (98.6%) and yields of 9–11 (30.8%, 42.1%, and

12.8% yield, respectively) were estimated based on the integration ratios of singlet signals for t-Bu

groups and the internal standard although the rest of quite minor products (13%) could not be

identified. Thus, the existing molar ratios of 8:9:10:11 were calculated from the above

1.6:35.4:48.3:14.7 (at 5 h) and 1.6:36.6:48.1:13.7 (at 28 h). However, after removal of volatiles, 1H

NMR spectrum indicated that the molar ratio changed to 0.9:26.1:72.3:0.7. neo-PenNH2 (1.2 M in

C6D6, 40 μL) was added to the sample containing complex 10 as the major, and 1H NMR analysis of

the resultant solution showed an increased ratio of 11: the complex distribution of 8:9:10:11 =

~0:7.8:70.7:21.5. These complexes were not attempted to isolate because they were waxy. The

structure of the major 10 was clearly determined by 1H and 13C NMR analysis while the structures of

minor 9 and 11 were proposed by 1H NMR analysis.

S13

The 1H NMR spectra of 9 and 10 showed signals for amido NH (triplet-like doublet of doublet) and

diastereotopic α-methylene protons (multiplet or doublet of doublet) whereas a doublet signal for

α-methylene protons and high-field shifted singlet signals for t-BuN and SiMe2 groups were

observed in the spectrum of 11, indicative of different environment of the supporting ligand from

that of 9 or 10.

[{Me2Si(C5Me4)(Nt-Bu)}Zr(NMe2)(NHCH2CMe3)] (9): 1H NMR (C6D6, 400 MHz): δ 3.58 (1H,

t-like dd, J = 7.2, 8.4 Hz, NH), 3.26–3.21 (2H, m, NHCH2), 2.83 (6H, s, NMe2), 2.14, 2.09, 1.99,

1.83 (3H × 4, s, C5Me4), 1.38 (9H, s, Nt-Bu), 0.89 (9H, s, NHCH2CMe3), 0.66 (3H, s, SiMeMe), 0.63

(3H, s, SiMeMe) ppm.

[{Me2Si(C5Me4)(Nt-Bu)}Zr(NHCH2CMe3)2] (10): 1H NMR (C6D6, 400 MHz): δ 3.40 (2H, t-like

dd, J = 7.6, 9.6 Hz, NH), 3.20 (2H, dd, J = 9.6, 12.4 Hz, NCHH), 3.08 (2H, dd, J = 7.6, 12.4 Hz,

NCHH), 2.15, 1.97 (6H × 2, s, C5Me4), 1.42 (9H, s, Nt-Bu), 0.90 (18H, s, NHCH2CMe3), 0.64 (6H, s,

SiMe2) ppm. 13C{1H} NMR (C6D6, 100 MHz): δ 127.5, 124.7, 100.3 (C5Me4), 62.2 (NHCH2), 54.8

(NCMe3), 35.2 (NCMe3), 33.6 (NHCH2CMe3), 27.5 (NHCH2CMe3), 13.9, 11.3 (C5Me4), 7.7 (SiMe2)

ppm.

[{Me2Si(C5Me4)(NHt-Bu)}Zr(NHCH2CMe3)3] (11): 1H NMR (C6D6, 400 MHz): δ 3.68 (3H, t, J =

8.8 Hz, NH), 3.30 (6H, d, J = 8.8 Hz, NHCH2), 2.28, 1.93 (6H × 2, s, C5Me4), 1.17 (9H, s, Nt-Bu),

0.97 (27H, s, NHCH2CMe3), 0.55 (6H, s, SiMe2) ppm.

Figure S4. Crystal Structure of 3a (ellipsoids set at 40% probability. Hydrogen atoms except amide

protons are omitted for clarity).

Zr3

Zr1

Zr2

H6

N7

N6

N5

N4

N3

N2

N1

H3

H2

H5

H7

C6

C5

C4

C3C2

C1

C7

C8

C9

C10

C11

C12

C13C14

C15

C16

C17

C18

C19

C20

C21

C22

C23

C24C25

C26

C27

C28

C29

C30

C31C32

C33

C34

C35

C37

C36

C38

C39

C40

C41

C42

C43

C44

C45

S14

Figure S5. Crystal Structure of 4a (ellipsoids set at 40% probability. Hydrogen atoms except amide

protons are omitted for clarity).

Figure S6. Crystal Structure of 5 (ellipsoids set at 40% probability. Hydrogen atoms are omitted for

clarity).

Zr1

Zr2

Zr3

N3

N2

N1

N4

N5

N6

H6

H2

C1

H5

C2

C3

C4

C5

C6

C7

C8

C9

C10 C11

C12C16

C13C14

C15

C17C18

C19

C20

C21

C22

C23

C24

C25

C26

C27C28

C29 C30

C31

C32

C33

C34

C36 C35

C37

C38

C39

C40

C41

C42

Zr1

Zr2

Zr3

N1

N2

N3

N4

N5

C1C2

C3C4

C5

C6

C7

C8

C9

C10

C11

C12

C13

C14

C15

C16

C17

C18

C19

C20

C21C22

C23

C24

C25

C26

C27

C28

C29C30

C31 C32

C33

C34

C35

C36

C37

C38

C39

C40

C21A

C20A

C19A

C18A

C17A

C12A

C13A

C14A

C15A

C16A

S15

Figure S7. Crystal Structure of 7 (ellipsoids set at 40% probability. Hydrogen atoms and solvent

molecule are omitted for clarity).

Zr2

N3

Zr1

Zr3

N1

N2

N4

N5

O1

C1

C2 C3

C4

C5

C6

C7

C8

C9

C10

C11

C12

C22C21

C13

C14

C15

C16

C17

C18

C19

C20

C23C24

C25C26

C27

C28

C29

C30

C31

C32

C33

C34

C35

C36

C37

C38

C39

C40

C41

C42

C43

C44

C45

C46

C47C48

C49C50

C51

S16

Figure S8. Representation of Effective Volumes (Veff) for Two Adjacent NMe2 Groups in The

Solid-State Structures of Reported Half-zirconocene Bis(amide)s, Me2Si(C5Me4)(E)Zr(NMe2)2 [E =

Nt-Bu (a), NCHMePh (b), NC6H4-4-CH=CH2 (c), N(2-Py) (d), C2B10H2 (e)] and Cp*(L)Zr(NMe2)2

[L = salicyloxazoline (f), (g)].

50.2 Å3 46.0 Å3

47.2 Å336.9 Å3

39.7 Å3

Zr Zr Zr

ZrZr

(a) (b) (c)

(d) (e)

molecule 133.4 Å3

molecule 233.4 Å3

molecule 134.5 Å3

molecule 230.6 Å3

(g) L = 2,4-di-tert-butyl-6-(4-(tert-butyl)-4,5-dihydrooxazol-2-yl)phenoxide

Zr1

Zr2

Zr1Zr2

Zr2

Zr1Zr2

Zr1

(f) L = 2,4-di-tert-butyl-6-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)phenoxide

S17

Thermolysis of 3 and 4

A mixture of 3a and 4a (57:43), prepared by reaction of 2 (13.4 µmol, 12 mg) and n-PrNH2 (77

µmol) in toluene followed by evaporation of volatiles, was dissolved in toluene (0.5 mL). The

mixture was heated at 100 ºC for 2 h. Volatiles were removed soon after the mixture was cooled to

room temperature. The product was dissolved in small amount of pentane while the solution became

red. Slow evaporation of pentane gave orange micro-crystals (8 mg, 68% yield). Formation of 12a

and 12a′ (~3.3:1) was confirmed by 1H NMR analysis. The equilibrium between 12a and 12a′ was

established by a SST experiment (Figure S9): Irradiation of signals of 12a at δ = 5.39 and –2.19 ppm

resulted in disappearance of the corresponding signals of 12a′ at δ = 5.59 and –0.95 ppm,

respectively.

[{LZr(η2-NCHCH2CH3)}(LZr)(LHZr)(μ-NHPr)] (12a): 1H NMR (C6D6, 400 MHz): δ 5.39 (1H,

dd, J = 6.8, 13.2 Hz, NCHHCH2C5Me4), 4.96–4.90 (1H, overlap, N′CHHCH2C5Me4), 4.95–4.86 (1H,

overlap, NCHHCH2C5Me4), 4.43 (1H, m, N′CHHCH2C5Me4), 3.31 (1H, m, NCH2CHHC5Me4), 2.85

(1H, m, HN″CHHCH2C5Me4), 2.84–2.76 (1H, overlap, HN1CHHCH2CH3), 2.82–2.72 (2H, overlap,

N′CH2CH2C5Me4), 2.81–2.71 (1H, overlap, NCH2CHHC5Me4), 2.45–2.37 (1H, overlap,

HN″CH2CHHC5Me4), 2.38–2.29 (1H, overlap, HN1CHHCH2CH3), 2.44, 2.33, 2.26, 2.22, 2.18, 2.13,

2.03, 2.03, 1.95, 1.93, 1.82, 1.80 (3H × 12, s, C5Me4 × 3), 2.24–2.01 (1H, overlap,

HN″CHHCH2C5Me4), 2.23–2.10 (1H, overlap, HN″CH2CHHC5Me4), 2.22–2.13 (1H, overlap,

N2CHCHHCH3), 2.15–2.09 (1H, overlap, N2CHCH2CH3), 1.35–1.10 (2H, m, HN1CH2CH2CH3),

1.15 (3H, t, J = 6.8 Hz, N2CH2CH2CH3), 0.90 (3H, t, J = 7.2 Hz, HN1CH2CH2CH3), 0.44 (1H, dd, J

= 2.8, 11.6 Hz, HN1CH2CH2CH3), 0.31 (1H, m, N2CHCHHCH3), –2.19 (1H, dd, J = 3.2, 13.2 Hz,

HN″CH2CH2C5Me4) ppm. 13C{1H} NMR (C6D6, 100 MHz): δ 132.2, 130.4, 126.6, 119.0, 118.9,

118.6, 118.4, 116.7, 116.3, 114.8, 114.7, 114.3, 114.2, 114.1, 113.9 (C5Me4 × 3), 91.2

(N2CHCH2CH3), 72.1 (NCH2CH2C5Me4), 65.1 (N′CH2CH2C5Me4), 55.6 (HN1CH2CH2CH3), 52.6

(HN″CH2CH2C5Me4), 38.6 (N2CHCH2CH3), 32.5 (HN1CH2CH2CH3), 31.3 (HN″CH2CH2C5Me4),

30.7 (NCH2CH2C5Me4), 30.3 (N′CH2CH2C5Me4), 19.5 (N2CHCH2CH3), 12.5 (HN1CH2CH2CH3),

13.0, 12.0, 11.6, 11.5, 11.13, 11.12, 11.0, 10.9, 10.8, 10.4, 10.4, 10.0 (C5Me4 × 3) ppm.

12a′: 1H NMR (C6D6, 400 MHz): δ 5.59 (1H, m), 5.01−4.84 (1H, overlap), 4.90−4.79 (1H, overlap),

4.60−4.45 (2H, m), 3.22−3.06 (2H, m), 2.83−2.74 (overlap), 2.31, 2.28, 2.24, 2.22, 2.21, 2.18, 2.14,

2.13, 1.99, 1.97, 1.86, 1.80 (3H × 12, s, C5Me4 × 3), 2.26−2.16 (overlap), 2.15−2.10 (1H, overlap,

η2-NCH), 1.21−1.13 (overlap), 0.52 (1H, m), −0.95 (1H, dd, J = 3.6, 14.4 Hz, NH) ppm. 13C{1H}

NMR (C6D6, 100 MHz): δ 131.7, 119.5, 118.9, 118.8, 117.7, 116.7, 116.6, 115.3, 115.2, 114.6, 114.4,

113.5 (C5Me4), 89.0 (η2-NCH), 71.9, 65.3, 56.6, 53.0 (NCH2), 38.9, 34.4, 32.4, 30.6, 30.4 (NCCH2),

19.1, 13.1, 12.7, 12.05, 12.01, 11.7, 11.4, 11.3, 11.2, 10.8, 10.5, 10.4, 10.2, 10.2 (C5Me4, NCCCH3)

ppm.

S18

Figure S9. 1H NMR spectra in the SST experiment (C6D6, 70 ºC): lower field region (a) before and

(b) after irradiation at δ = 5.39 ppm (signal for NCHHCH2C5Me4 of 12a), and higher field region (c)

before and (d) after irradiation at δ = –2.19 ppm (signal for HN″CH2CH2C5Me4 of 12a).

Zr N H

Zr

N Zr

N

H

H

H

H

H

H

1.93

2.182.03

2.44

2.85

2.24-2.01

2.131.82

2.322.22

2.03

1.802.26

1.95

5.39

4.95-4.86

4.43

4.96-4.90

2.82-2.72HH

HH

3.31,2.81-2.71

H H

2.45-2.372.23-2.10(a) (b)

-2.19Zr N H

Zr

N Zr

N

H

H

H

H

H

H

HH

HH

H H

NHN

1.80

2.26

1.15

0.90

0.44

2.22

-2.19

4.95-4.86

Figure S10. The most plausible structure of 12a: (a) assignment of resonances of the supporting

ligands (green) and their arrangement by HSQC, HMBC, and ROESY (blue arrows), and (b)

arrangement of other ligand fragments by ROESY (blue arrows).

5.00 4.505.50

irradiation

-1.50 -2.00 -2.50-0.500.50 0.00 -1.00

irradiation

(a)

(c)

(b)

(d)

S19

[{LZr(η2-NCHCH3)}(LZr)(LHZr)(μ-NHEt)] (12b): 1H NMR (C6D6, 400 MHz): δ 5.42 (1H, ddd,

J = 1.6, 8.0, 12.8 Hz, NCHHCH2C5Me4), 4.99–4.87 (1H, overlap, NCHHCH2C5Me4), 4.96–4.85 (1H,

overlap, N′CHHCH2C5Me4), 4.50–4.38 (1H, overlap, N′CHHCH2C5Me4), 3.38–3.26 (1H, m,

NCH2CHHC5Me4), 2.95–2.93 (1H, m, HN1CHHCH3), 2.89–2.80 (1H, m, HN″CHHCH2C5Me4),

2.86–2.76 (2H, overlap, N′CH2CH2C5Me4), 2.84–2.73 (1H, overlap, NCH2CHHC5Me4), 2.42–2.35

(1H, overlap, HN″CH2CHHC5Me4), 2.45, 2.36, 2.31, 2.20, 2.19, 2.10, 2.06, 2.03, 1.94, 1.92, 1.82,

1.80 (3H × 12, s, C5Me4 × 3), 2.42–2.32 (1H, overlap, HN1CHHCH3), 2.27–2.17 (1H, overlap,

N2CHCH3), 2.25–2.19 (1H, overlap, HN″CH2CHHC5Me4), 2.15–1.94 (1H, overlap,

HN″CHHCH2C5Me4), 1.46 (3H, d, J = 6.0 Hz, N2CHCH3), 0.97 (3H, t, J = 7.0 Hz, HN1CH2CH3),

0.24 (1H, dd, J = 2.8, 11.6 Hz, HN1CH2CH3), –2.20 (1H, dd, J = 3.2, 14.0 Hz, HN″CH2CH2C5Me4)

ppm. 13C{1H} NMR (C6D6, 100 MHz): δ 132.1, 130.3, 126.8, 119.2, 119.1, 118.9, 118.4, 116.8,

116.5, 115.4, 115.0, 114.54, 114.51, 114.1, 113.8 (C5Me4 × 3), 80.9 (N2CHCH3), 72.0

(NCH2CH2C5Me4), 64.9 (N′CH2CH2C5Me4), 52.4 (HN″CH2CH2C5Me4), 47.3 (HN1CH2CH3), 31.3

(HN″CH2CH2C5Me4), 30.6 (NCH2CH2C5Me4), 30.4 (N′CH2CH2C5Me4), 29.9 (N2CHCH3), 24.2

(HN1CH2CH3), 13.1, 12.0, 11.7, 11.6, 11.5, 11.17, 11.16, 11.14, 11.08, 11.0, 10.2, 10.1 (C5Me4 × 3)

ppm.

12b′: Partial 1H NMR (C6D6, 400 MHz): δ 5.66 (1H, m), 4.96 (1H, overlap), 4.82 (1H, m), 4.57 (1H,

td, J = 8.0, 12.8 Hz), 4.01 (1H, dd, J = 6.8, 12.0 Hz), 3.71 (1H, dd, J = 7.2, 12.0 Hz), 3.17 (1H, td, J

= 8.0, 13.2 Hz), 2.85–2.75 (overlap), 2.72–2.60 (overlap), 2.37, 2.31, 2.28, 2.22, 2.21, 2.15, 2.04,

1.99, 1.97, 1.85, 1.84, 1.81 (3H × 12, s, C5Me4 × 3), 2.35–2.25 (1H, overlap, NCHCH3), 2.28–2.14

(overlap). 1.57 (3H, d, J = 6.0 Hz, NCHCH3), 1.20–1.15 (overlap), 1.01 (3H, t, J = 7.2 Hz,

NCH2CH3), –0.91 (1H, dd, J = 3.2, 14.0 Hz, NH) ppm. 13C{1H} NMR (C6D6, 100 MHz): δ 131.3,

130.8, 127.2, 119.7, 119.5, 117.9, 117.1, 116.8, 116.6, 115.23, 115.16, 114.9, 114.4, 113.7 (C5Me4 ×

3), 78.6 (NCHCH3), 71.9 (NCH2), 65.1 (NCH2), 53.2 (NCH2), 48.3 (NCH2), 31.4 (NCH2CH2), 30.6

(NCH2CH2), 30.5 (NCH2CH2), 30.2 (NCHCH3), 23.9 (NCH2CH3), 13.2, 12.1, 11.9, 11.65, 11.58,

11.4, 11.3, 11.2, 11.1, 10.5, 10.3, 10.2 (C5Me4 × 3) ppm.

Synthesis of 13c and 14a

Substrate 13c was synthesized via Gabriel method:

A solution of 3,3-dimethyl-1-propyne (15 mmol, 1.84 mL) in THF (20 mL) was cooled to –78 °C

under argon, and a solution of BuLi (2.5 M in hexane, 6.3 mL) was added. After stirred at –78 °C for

S20

15 min and at 0 °C for 0.5 h, 1,3-diiodopropane (17.4 mmol, 2.0 mL) and HMPA (3.0 mL) were

added at –78 °C. The mixture was allowed to slowly warm to room temperature and stirred for 8 h.

After workup, the crude monoiodide was obtained by distillation (76–78 °C /0.001 MPa) (2.5 g, 69%

purity).

The monoiodide (~6 mmol, 1.6 g) and potassium phthalimide (8.5 mmol, 1.6 g) were dissolved in

DMF (10 mL). The mixture was heated at 145 °C for 20 h. The resultant mixture, after cooled to

room temperature, was dropped into a vigorously stirred ice water, giving white precipitate. The

precipitate was obtained by filtration, washed with H2O, and air-dried (1.1 g). The solid was

dissolved in MeOH (20 mL) and H2NNH2•H2O (17 mmol, 0.85 g) was added. The mixture became

suspended while it was heated at reflux for 1 h. The insoluble solid was removed by filtration, and

the product was separated by extraction under acidic and basic conditions. Distillation of the

colorless oil at 90–110 °C/0.0016 MPa gave 13c (0.10 g, 12% yield for the monoiodide). 1H NMR

(CDCl3, 400 MHz): δ 2.77 (2H, t, J = 7.0 Hz, NCH2), 2.19 (2H, t, J = 7.0 Hz, NCH2CH2CH2) 1.59

(2H, quint-like tt, J = 7.0 Hz, NCH2CH2CH2), 1.23 (2H, br, NH2), 1.17 (9H, s, CMe3) ppm. 1H NMR

(C6D6, 400 MHz): δ 2.55 (2H, t, J = 7.0 Hz, NCH2), 2.11 (2H, t, J = 7.0 Hz, NCH2CH2CH2) 1.40

(2H, quint-like tt, J = 7.0 Hz, NCH2CH2CH2), 1.22 (9H, s, CMe3), 0.41 (2H, br, NH2) ppm. 13C{1H}

NMR (CDCl3, 100 MHz): δ 89.4 (CH2C≡C), 77.7 (CH2C≡C), 41.3 (NCH2), 32.9 (NCH2CH2), 31.3

(CMe3), 27.3 (CMe3), 16.1 (CH2C≡C) ppm.

Synthesis of 14a is outlined as follows:

4-Cyano-4-methyl-1-pentyne (7.5 mmol, 0.80 g)5 was dissolved in THF (15 mL) under nitrogen

atmosphere. The solution was cooled to –78 °C, and a solution of BuLi in hexane (2.5 M, 8.8 mmol)

was added. After stirring at this temperature for 0.5 h and at 0 °C for 10 min, HMPA (2.0 mL) and

iodoethane (8.8 mmol, 0.71 mL) were added subsequently. The mixture was allowed to warm to

room temperature and continued to stir for 8 h. The reaction was then quenched by addition of

ice-water. The product was extracted with ether, and ethereal layer was washed with H2O. The

organic layer was dried over Na2SO4. Evaporation of solvent and distillation at 78–82 °C/21 mbar

gave the desirable nitrile as a colorless oil (0.67 g, 62%). 1H NMR (CDCl3, 400 MHz): δ 2.44 (2H, t,

J = 2.4 Hz, CH2C≡C), 2.21 (2H, tq, J = 2.4, 7.6 Hz, CH2CH3), 1.42 (6H, s, NCCMe2), 1.15 (3H, t, J

= 7.6 Hz, CH2CH3) ppm. 13C NMR (CDCl3, 100 MHz): δ 124.5 (s, CN), 86.0 (s, C≡C), 73.5 (s,

C≡C), 32.5 (s, CCN), 31.4 (t, J = 134 Hz, CH2), 25.9 (q, J = 130 Hz, CMe2), 14.1 (q, J = 128 Hz,

CH2CH3), 12.4 (t, J = 131 Hz, CH2CH3) ppm.

5 Stevens, R. V.; DuPree, Jr., L. E.; Edmonson, W. L.; Magid, L. L.: Wentland, M. P. J. Am. Chem. Soc. 1971, 93, 6637.

S21

LiAlH4 (5.3 mmol, 0.20 g) was suspended in Et2O (15 mL) under nitrogen atmosphere. The above

nitrile (4.4 mmol, 0.60 g) was addd at 0 °C in 10 min. The mixture was warmed to r.t. and then

heated to reflux. After 3 h, the reaction mixture was allowed to cool to 0 °C. Na2SO4 (22 mmol, 3.10

g) and NaF (22 mmol, 0.92 g) were added with stirring, subsequently, H2O (0.3 mL) was syringed in

carefully. After filtration of the slurry, the filtrate was treated with HCl. The ethereal layer was

removed by decantation, and the residue was washed with hexane. The residue was basified with aq.

NaOH and the product was extracted with hexane. The organic layer was separated and dried over

NaOH pellets. Most of the solvent was removed under reduced pressure (25 °C/80 mbar). The

desirable 14a was distilled at 70 °C/20 mbar (0.12 g, 20%). 1H NMR (CDCl3, 400 MHz): δ 2.53 (2H,

s, CH2N), 2.15 (2H, dq, J = 2.4, 4.8 Hz, CH2CH3) 2.04 (2H, t, J = 2.4 Hz, CH2C≡C), 1.25 (2H, br,

NH2), 1.11 (3H, t, = 4.8 Hz, CH2CH3), 0.91 (6H, s, CCMe2) ppm.

Catalytic Cyclization of Aminoalkynes 13 and 14

In the glovebox, complex 2 (2.5–4.7 μmol) was weighed into the NMR tube with a Teflon valve. The

sample was dissolved in C6D6 (0.45 mL) with (Me3Si)2CH2 (trace amount) as an internal standard. A

solution of the aminoalkyne (0.59–1.30 M in C6D6, ca 20 equiv) was syringed into the NMR tube.

NMR spectra were also recorded before addition of the substrate and heating the sample tube to

monitor the reaction progress. The products 15a, 15b, and 16b were identified by 1H NMR spectra

reported in the literature.6 The novel cyclization products 15c and 16a were identified by spectral

comparison with those analogs, respectively.

5-Neopentyl-3,4-dihydro-2H-pyrrole (15c): 1H NMR (C6D6, 400 MHz): δ 3.77 (2H, quint-t-like ttt,

J = 1.8, 7.2 Hz, NCH2), 2.15 (2H, br, CCH2CMe3), 2.07 (2H, tt, J = 1.8, 7.8 Hz, N=CCH2), 1.44 (2H,

tt, J = 7.2, 7.8 Hz, NCH2CH2CH2), 1.01 (9H, s, CMe3) ppm. 13C{1H} NMR (C6D6, 100 MHz): δ

174.9 (N=C), 61.5 (NCH2CH2CH2), 46.9 (CH2CMe3), 40.1 (NCH2CH2CH2), 31.3 (CH2CMe3), 30.2

(CH2CMe3), 23.1 (NCH2CH2CH2) ppm.

3,3-Dimethyl-5-propyl-3,4-dihydro-2H-pyrrole (16a): 1H NMR (C6D6, 400 MHz): δ 3.55 (2H,

quintet-like tt, J = 1.6 Hz, NCH2), 2.12 (2H, dt, J = 1.6, 7.2 Hz, CH2CH2CH3), 1.93 (2H, t, J = 1.6

Hz, N=CCH2) 1.59 (2H, sextet-like dq, J = 7.2 Hz, CH2CH2CH3), 0.89 (3H, t, J = 7.2 Hz,

CH2CH2CH3), 0.87 (6H, s, CMe2) ppm. 13C{1H} NMR (C6D6, 100 MHz): δ 175.8 (N=C), 74.8

(CH2N=C), 52.4 (N=CCH2), 38.3 (CMe2), 36.3 (CH2CH2CH3), 28.0 (CMe2), 19.9 (CH2CH2CH3),

14.2 (CH2CH2CH3) ppm.

6 (a) McGrane, P. L.; Jensen, M.; Livinghouse, T. J. Am. Chem. Soc. 1992, 114, 5459. (b) Kondo, T.; Okada, T.; Mitsudo, T. J. Am. Chem. Soc. 2001, 124, 186.

S22

Figure S11. 1H NMR spectra (C6D6, t = 0.5 h, δ = 4.90–2.85 ppm) when complex 2 and excess

amounts of 13 were mixed at 25 °C; (a) with 13a, (b) with 13b, and (c) with 13c.

Stoichiometric Reaction of 2 and 13c

(i) Characterization of 17

Complex 2 (5.6 μmol, 5.0 mg) and 13c (42 μmol, 7.5 equiv) were dissolved in C6D6 (0.5 mL) at

25 °C, and the reaction was monitored by 1H NMR analysis. As observed in the reaction with

n-PrNH2 or catalytic reaction at 25 °C, the 1H NMR spectrum recorded at the initial stage (0.5 h)

showed quantitative formation of the kinetically favored structure (17ckinetic), containing four

molecules of 13c. After 20 h, this turned to the thermodynamically stable structure (17c). These two

structures were characterized only by NMR spectroscopy, and isolation of 17c was not attempted.

17ckinetic (t = 0.5 h at 25 °C): Partial 1H NMR (C6D6, 400 MHz): δ 4.74–4.65 (2H, m), 4.35 (1H, dd, J

= Hz), 3.96–3.88 (1H, m), 3.71–3.46 (3H, m), 3.44–3.26 (3H, m), 3.26–2.87 (5H, m), 2.80–2.68 (1H,

m), 2.51–2.48 (1H, m), 2.35 (4H, m), 2.28, 2.20, 2.20, 2.15, 2.14, 2.12, 2.05, 1.961, 1.955, 1.95,

1.933, 1.927 (3H × 12, s, C5Me4 × 3), 1.74–1.62 (8H, m), 1.304, 1.302, 1.284, 1.281 (9H × 4, s,

CMe3 × 4), 0.88 (1H, m), 0.75 (1H, m), 0.29 (1H, m) ppm.

[(LZrNHR)(LHZrNHR)(LHZr)(μ-NHR)(μ3-NR)] (R = CH2CH2CH2C≡CBu-t) (17c) (t = 20 h at

25 °C): Following partial signal assignment was made by COSY, HMQC, and HMBC experiments.

Partial 1H NMR (C6D6, 400 MHz): δ 4.45 (1H, dd, J = 7.2, 12.0 Hz, NCHH), 4.37 (1H, t-like dd, J =

8.0 Hz, NH), 4.25 (1H, dd, J = 4.6, 11.8 Hz, NH), 4.08 (1H, t-like dd, J = 11.6 Hz, NCHH), 3.95 (2H,

m, NCH2), 3.81 (1H, m, NCHH), 3.65–3.45 (5H, m, NCH2 + NCCH2), 3.37 (2H, m, NCH2), 2.93

(2H, m, NCH2), 2.50–2.20 (2H × 4, m, NCH2CH2CH2), 2.29, 2.23, 2.20, 2.16, 2.15, 2.14, 2.14, 2.10,

(a)

(b)

(c)

S23

2.05, 1.96, 1.91, 1.87 (3H × 12, s, C5Me4 × 3), 1.95–1.55 (8H, m, NCH2CH2CH2), 1.31, 1.30, 1.29,

1.28 (9H × 4, s, CMe3 × 4), 0.87 (1H, m), 0.73 (1H, dd, J = 6.6, 12.6 Hz), 0.32 (1H, t-like dd, J = 7.0

Hz, NH) ppm. 13C{1H} NMR (C6D6, 100 MHz): δ 129.7, 128.7, 122.4, 122.2, 118.5, 118.1, 117.74,

117.69, 116.7, 116.4, 116.2, 115.4, 115.0, 114.5, 113.8 (C5Me4 × 3), 89.5, 89.0, 88.84, 88.78

(CH2C≡C × 4), 79.6, 79.2, 78.9, 77.9 (CH2C≡C × 4), 63.1, 60.2, 57.5, 55.7, 53.0, 51.8, 51.2

(NCH2CH2C5Me4 × 3 + NCH2CH2CH2 × 4), 36.40, 36.37, 36.3, 35.8 (NCH2CH2CH2 × 4), 31.83,

31.81, 31.79, 31.7 (CMe3 × 4), 31.4, 31.2, 28.7 (NCH2CH2C5Me4 × 3), 27.7, 27.6 (CMe3 × 4), 18.7,

18.0, 17.2, 17.1 (CH2C≡C × 4), 13.3, 13.3, 13.2, 12.5, 12.03, 12.00, 11.9, 11.7, 11.6, 11.4, 11.3, 10.9

(C5Me4 × 3) ppm.

Figure S12. Partial 1H NMR spectra of the reaction of 2 and 13c (C6D6, 25 °C): Open circles and

solid triangles indicate signals for C5Me4 groups in 17ckinetic and 17c, respectively.

4.50 4.00 3.50 3.00 2.30 2.20 2.00 1.902.10

Me2NH

t = 0.5 h

t = 20 h

13c

S24

Figure S13. Comparison of 1H NMR partial spectra of complexes 3a and 17c (C6D6, 25 °C):

Characteristic NCH2 and terminal NH protons are indicated in red and blue, respectively.

(ii) Thermolysis of 17c

Complexes 18c (and 18c′) were synthesized by thermolysis of 17c analogously for the synthesis of

12 (and 12′). First, stoichiometric reaction of 2 (16.8 μmol, 15 mg) with 13c (5 equiv) was carried

out in toluene. After the solution was stood at 25 °C for 21 h, all volatiles were removed under

reduced pressure, and the residue was dissolved in C6D6 and 17c was found to be the major product.

The solution was heated at 100 °C for 1 h while the solution became orange. 1H NMR analysis of the

mixture showed formation of complex 18c (81% yield), 18c′ (19% yield), and 15c (~200% yield

based on complex 17c). Evaporation of volatiles and dryness in vacuo gave a mixture of 18c and

18c′ as a waxy oil (18c/18c′ = 4.3:1). The NMR signal assignment was made by COSY, HSQC, and

HMBC experiments and the structure of major 18c was determined by comparison of the NMR

spectra with those of 12a.

[{LZr(η2-NCHCH2CH2C≡CBu-t)}(LZr)(LHZr)(μ-NHCH2CH2CH2C≡CBu-t)] (18c): 1H NMR

(C6D6, 400 MHz): δ 5.34 (1H, dd, J = 7.6, 12.8 Hz, NCHHCH2C5Me4), 4.92 (1H, m,

N′CHHCH2C5Me4), 4.81 (1H, m, NCHHCH2C5Me4), 4.48−4.35 (1H, overlap, N′CHHCH2C5Me4),

3.25 (1H, m, NCH2CHHC5Me4), 3.00 (1H, m, HN1CHHCH2CH2), 2.85 (1H, m,

HN″CHHCH2C5Me4), 2.81−2.72 (2H, overlap, N′CH2CH2C5Me4), 2.75−2.65 (1H, overlap,

NCH2CHHC5Me4), 2.50−2.34 (1H, overlap, N2CHCHHCH2), 2.36−2.22 (1H, overlap,

ppm (t1)2.002.503.003.504.004.50

1H + 1H 1H 2H1H 1H × 3+ 2H

1H 1H 1H 1H 1H

1H 1H 1H 2H1H 2H 1H 5H 2H

▢

*

▢▴

containing 13c (▢) and HNMe2 (▴)

▴

containing H2NPr (*) and HNMe2 (▴)

S25

HN1CHHCH2CH2), 2.32−2.22 (1H, overlap, N2CHCH2CH2), 2.30−2.09 (1H, overlap,

HN″CHHCH2C5Me4), 2.28−2.20 (1H, overlap, HN″CH2CHHC5Me4), 2.20−2.11 (1H, overlap,

HN″CH2CHHC5Me4), 2.17−2.12 (4H, overlap, HN1CH2CH2CH2 and N2CHCH2CH2), 2.42, 2.27,

2.26, 2.23, 2.22, 2.10, 2.03, 2.03, 1.94, 1.90, 1.85, 1.81 (3H × 12, s, C5Me4 × 3), 1.58−1.47 (1H,

overlap, HN1CH2CHHCH2), 1.42−1.25 (1H, overlap, HN1CH2CHHCH2), 1.28, 1.27 (9H × 2, s,

CMe3 × 2), 0.58 (1H, m, N2CHCHHCH2), 0.37 (1H, dd, J = 2.9, 11.8 Hz, HN1CH2CH2CH2), –2.19

(1H, m, HN″CH2CH2C5Me4) ppm. 13C{1H} NMR (C6D6, 100 MHz): δ 132.2, 130.6, 126.7, 119.3,

119.1, 118.8, 118.5, 116.9, 116.4, 115.1, 115.0, 114.5, 114.3, 114.3, 114.2 (C5Me4 × 3), 89.3, 89.1

(CH2C≡C × 2), 87.9 (N2CHCH2CH2), 79.9, 79.0 (CH2C≡C × 2), 72.3 (NCH2CH2C5Me4), 65.1

(N′CH2CH2C5Me4), 52.7 (HN″CH2CH2C5Me4 and HN1CH2CH2CH2), 45.3 (N2CHCH2CH2), 39.1

(HN1CH2CH2CH2), 31.8, 31.7 (CMe3 × 2), 31.2 (HN″CH2CH2C5Me4), 30.6 (NCH2CH2C5Me4), 30.2

(N′CH2CH2C5Me4), 27.70, 27.68 (CMe3 × 2), 17.5 (CH2C≡C × 2), 13.0, 12.0, 11.6, 11.5, 11.4, 11.09,

11.08, 11.02, 10.98, 10.9, 10.5, 10.0 (C5Me4 × 3) ppm.

Figure S14. Comparison of 1H NMR partial spectra of complexes 12a and 18c (C6D6, 25 °C):

Characteristic NCH2(support) and bridging NH protons are indicated in red and blue, respectively.

Semi-catalytic Reaction of 2 and 14b

Complex 2 (9.6 μmol, 8.6 mg) and the internal standard were dissolved in C6D6 (0.8 mL). After the 1H NMR spectrum was recorded, in the glovebox, a solution of 14b (1.2 M in C6D6, 54 μL) was

syringed into the NMR tube. The reaction was monitored at 25 °C by NMR spectroscopy (Figure 5).

By the nearly complete consumption of 14b, intermediate 19b was observed mainly. After that, 19b

ppm (t1)-2.0-1.00.01.02.03.04.05.0

containing 15c (▢) and

(Me3)2CH2 (*) (standard)

▢

▢

*

*

▢

▢

1H

1H1H

1H

1H 1H1H 1H 1H1H

1H 1H1H 1H 1H1H

S26

was gradually replaced by 20b. Complexes 19b and 20b were only characterized by NMR analysis

because of their thermal instability.

[(LZr)2(LZrNMe2)(μ-NCH2CMe2CH2C≡CPh)] (19b): 1H NMR (C6D6, 400 MHz): δ 7.46–7.43

(2H, overlap, Ph-H, ortho), 7.02–6.95 (3H, overlap, Ph-H, meta and para), 5.07 (2H, m, NCHHCH2

+ N′CHHCH2), 4.93 (1H, dd, J = 6.6, 12.4 Hz, NCHHCH2), 4.78 (2H, m, N″CH2CH2), 4.47 (1H, dd,

7.2, 12.4 Hz, N′CHHCH2), 2.99–2.88 (1H, overlap, NCH2CHH), 2.85–2.73 (1H, overlap,

NCH2CHH), 2.86–2.65 (2H, overlap, N″CH2CH2), 2.80 (6H, s, NMe2), 2.80–2.67 (1H, overlap,

N′CH2CHH), 2.63–2.51 (1H, overlap, N′CH2CHH), 2.51 (1H, d, J = 12.0 Hz, NCHHCMe2CH2),

2.34 (1H, d, J = 12.4 Hz, NCH2CMe2CHH), 2.26, 2.21, 2.18, 2.18, 2.15, 2.14, 2.09, 2.04, 1.97, 1.96,

1.95, 1.92 (3H × 12, s, C5Me4 × 3), 1.91 (1H, overlap, NCH2CMe2CHH), 1.38 (1H, d, J = 12.0 Hz,

NCHHCMe2CH2) ppm.

Figure S15. Comparison of 1H NMR partial spectra of complexes 5 and 19b (C6D6, 25 °C):

Characteristic NCH2CH2(support) and NMe2 protons are indicated in red and blue, respectively.

[(LZrNMe2)2{LZr(2-benzylidene-4,4-dimethylpyrrolidide)}] (20b): 1H NMR (C6D6, 400 MHz): δ

7.36 (2H, d, J = 4.3 Hz, Ph-H), 7.14 (2H, overlap, Ph-H), 7.02 (1H, overlap, Ph-H), 5.25 (1H, br s,

C=CHPh), 4.83 (1H, m, NCHHCH2), 4.51 (1H, dt-like ddd, J = 5.6, 11.6 Hz, N′CHHCH2), 4.36 (1H,

dd, J = 6.6, 12.8 Hz, N′CHHCH2), 4.29 (1H, br, N″CHHCH2), 4.03 (1H, br, N″CHHCH2), 3.89 (1H,

br, NCHHCH2), 3.27 (1H, d, J = 10.4 Hz, C5HH, pyrrolidide), 3.15 (1H, d, J = 10.4 Hz, C5HH,

pyrrolidide), 2.94–2.80 (1H, overlap, N′CH2CHH), 2.89 (6H, s, NMe2), 2.78–2.68 (2H, overlap,

NCH2CH2), 2.76–2.64 (1H, overlap, N′CH2CHH), 2.74 (6H, s, NMe2), 2.67–2.49 (2H, overlap,

ppm (t1)2.002.503.003.504.004.505.00

*

*

****

1H1H + 1H + 1H + 2H

NMe2 (6H)

1H + 1H 1H 2H 1H

1H + 1H 1H 2H 1H

NMe2 (6H)

containing 14b (*) and 16b (**)

1H1H + 1H + 2H + 1H

S27

N″CH2CH2), 2.60 (2H, br, C3H2, pyrrolidide), 2.13, 2.09, 2.08, 2.041, 2.036, 1.99, 1.97, 1.96, 1.95,

1.94, 1.92, 1.89 (3H × 12, s, C5Me4 × 3), 1.13 (3H, s, CMeMe), 1.09 (3H, s, CMeMe) ppm. 13C{1H}

NMR (C6D6, 100 MHz): δ 160.8 (C2, pyrrolidide), 143.0, 128.9, 125.5, 121.2 (Ph), 130.6, 129.0,

126.4, 121.2, 120.8, 120.5, 120.4, 119.3, 119.0, 118.8, 117.6, 116.0, 115.6, 114.3 (C5Me4 × 3), 95.5

(C=CHPh), 66.6 (C5, pyrrolidide), 62.8 (NCH2CH2), 61.5 (N″CH2CH2), 59.3 (N′CH2CH2), 48.6 (C3,

pyrrolidide), 46.3 (NMe2), 46.1 (NMe2), 38.7 (C4, pyrrolidide), 29.6 (N″CH2CH2), 29.4 (N′CH2CH2),

28.9 (NCH2CH2), 28.59 (CMeMe), 28.56 (CMeMe), 13.1, 12.4, 11.9, 11.70, 11.66, 11.66, 11.5, 11.1,

11.0, 10.67, 10.65, 10.3 (C5Me4 × 3) ppm. One Cp-ring carbon resonance of the NCH2CH2C5Me4

fragment is missing, probably, due to signal broadening.

Figure S16. The most plausible structure of 20b: (a) assignment of resonances of the supporting

ligands (green) and their arrangement by HSQC, HMBC, and ROESY (blue arrows), and (b)

arrangement of other ligand fragments by ROESY (blue arrows).

S28

Table S1. Crystal, measurement, refinement data for complexes 2, 3a, 4a, 4c, 5, 6b, and 7.

Complex 2 3a 4a

Empirical formula C39H66N6Zr3 C45H81N7Zr3 C42H72N6Zr3

Formula weight 892.63 993.82 934.71

Temperature [K] 123(2) 123(2) 123(2)

Crystal system Orthorhombic Monoclinic Triclinic

Space group Pna21 Cc P-1

a [Å] 22.5649(8) 11.5237(5) 11.4107(5)

b [Å] 10.0550(3) 22.4323(9) 11.8142(7)

c [Å] 18.0848(7) 17.9161(7) 18.1472(8)

α [°] 90 90 83.119(2)

β [°] 90 93.203(2) 81.923(1)

γ [°] 90 90 63.834(2)

V [Å3] 4103.3(2) 4624.1(3) 2169.3 (2)

Z 4 4 2

ρ [Mg m-3] 1.445 1.428 1.431

μ [mm-1] 0.782 0.702 0.743

F(000) 1848 2080 972

Crystal size 0.43 x 0.12 x 0.10 0.22 x 0.05 x 0.04 0.18 x 0.12 x 0.10

θ range [°] 3.161 to 27.482 3.098 to 27.482 3.072 to 27.481

Index ranges -25<=h=<29 -14<=h=<13 -13<=h=<14

-13<=k=<12 -29<=k=<29 -15<=k=<15

-23<=l=<23 -23<=l=<23 -23<=l=<23

Refl. Collected 36849 22594 21699

Indep. Refl. [R(int)] 9387 [0.0784] 22242 [0.0467] 9869 [0.0298]

Abs. correction Empirical Empirical Empirical

Max. and min. transmission 1.0000, 0.1568 1.0000, 0.6975 1.0000, 0.6397

Data / restraints / parameters 9387 / 1 / 470 9758 / 12 / 527 9869 / 9 / 481

GOF on F2 1.012 0.962 1.030

R1 [I>2σ(I)] 0.0459 0.0257 0.0644

wR2 (all data) 0.1091 0.0541 0.1771

Largest diff. peak and hole [eÅ-3] 1.037, -1.182 0.769, -0.547 5.846, -1.143

S29

Table S1. (continued)

Complex 4c 5 6b

Empirical formula C45H78N6Zr3 C40H65N5Zr3 C58H71Br3N6Zr3

Formula weight 976.79 889.63 1365.59

Temperature [K] 123(2) 159(2) 123(2)

Crystal system Monoclinic Monoclinic Monoclinic

Space group P21/c P21/n P21/n

a [Å] 21.1636(10) 11.9363(4) 12.2505(5)

b [Å] 12.1570(7) 17.9407(5) 22.8392(9)

c [Å] 18.4466(8) 19.9910(6) 19.9157(7)

α [°] 90 90 90

β [°] 105.387(2) 105.446(1) 96.852(1)

γ [°] 90 90 90

V [Å3] 4575.9(4) 4126.4(2) 5532.4(4)

Z 4 4 4

ρ [Mg m-3] 1.418 1.432 1.640

μ [mm-1] 0.708 0.776 2.765

F(000) 2040 1840 2744

Crystal size 0.28 x 0.10 x 0.05 0.14 x 0.12 x 0.10 0.13 x 0.08 x 0.07

θ range [°] 2.995 to 26.368 3.103 to 27.459 3.067 to 26.371

Index ranges -26<=h=<26 -15<=h=<15 -15<=h=<15

-15<=k=<15 -23<=k=<23 -28<=k=<28

-21<=l=<23 -25<=l=<25 -24<=l=<22

Refl. Collected 65906 40547 47929

Indep. Refl. [R(int)] 9338 [0.0628] 9422 [0.1040] 11297 [0.1454]

Abs. correction Empirical Empirical Numerical

Max. and min. transmission 1.0000, 0.7219 1.0000, 0.6916 0.8154, 0.7379

Data / restraints / parameters 9338 / 0 / 517 9422 / 0 / 445 11297 / 0 / 654

GOF on F2 1.029 1.039 1.030

R1 [I>2σ(I)] 0.0347 0.0549 0.0596

wR2 (all data) 0.0812 0.1097 0.1665

Largest diff. peak and hole [eÅ-3] 0.702, -0.538 0.908, -0.740 0.959, -1.054

S30

Table S1. (continued)

Complex 7

Empirical formula C58H89N5O1Zr3

Formula weight 1146.00

Temperature [K] 123(2)

Crystal system Triclinic

Space group P-1

a [Å] 12.8478(8)

b [Å] 13.0149(9)

c [Å] 18.0443(11)

α [°] 112.234(2)

β [°] 101.979(2)

γ [°] 92.165(2)

V [Å3] 2709.4(3)

Z 2

ρ [Mg m-3] 1.405

μ [mm-1] 0.610

F(000) 1200

Crystal size 0.20 x 0.05 x 0.04

θ range [°] 3.124 to 27.477

Index ranges -16<=h=<16

-16<=k=<16

-23<=l=<23

Refl. Collected 27169

Indep. Refl. [R(int)] 12318 [0.0967]

Abs. correction Empirical

Max. and min. transmission 1.0000, 0.5101

Data / restraints / parameters 12318 / 0 / 579

GOF on F2 1.064

R1 [I>2σ(I)] 0.0638

wR2 (all data) 0.1752

Largest diff. peak and hole [eÅ-3] 1.032, -1.113

S31

ppm (t1)3.504.004.50

4.7

43

4.7

27

4.7

16

4.7

09

4.7

00

4.6

93

4.6

83

4.6

67

4.6

19

4.6

08

4.6

01

4.5

92

4.5

85

4.5

75

4.5

59

4.2

56

4.2

42

4.2

31

4.2

25

4.2

17

4.2

11

4.2

01

4.1

86

3.9

40

3.9

35

3.9

26

3.9

21

3.9

09

3.9

03

3.8

96

3.8

90

3.6

21

3.6

06

3.5

87

3.5

73

3.4

86

3.4

71

3.4

51

3.4

38

3.4

35

1.0

0

1.0

0

1.0

1

1.0

0

0.9

8

1.0

3

1H NMR (C6D6, 400 MHz)

solvent

ppm (t1)0.01.02.03.04.05.06.07.08.0

2.9

73

2.9

48

2.7

61

1.0

0

1.0

0

1.0

11

.00

0.9

81

.03

12

.34

5.5

35

.57

2.9

35

.67

5.6

32

.92

5.5

02

.60

2.5

42

.51

2.5

3

ppm (t1)1.9001.9502.0002.0502.100

2.1

24

2.1

00

2.0

96

2.0

50

2.0

14

1.9

78

1.9

64

1.9

36

1.9

22

1.9

10

2.9

3

5.6

7

5.6

3

2.9

2

5.5

02

.60

2.5

42

.51

2.5

3

2

Zr NMe2N

Zr

N

NMe2

Zr

N

NMe2

COSY of 2 (C6D6, 400 MHz)

ppm (t2)2.503.003.504.004.50

2.50

3.00

3.50

4.00

4.50

ppm (t1

S32

ppm (t1)050100150

130

.35

130

.04

125

.93

120

.87

119

.64

118

.73

118

.62

118

.35

117

.79

116

.55

115

.99

114

.94

114

.20

113

.73

113

.48

60.

68

59.

66

58.

54

46.

70

46.

10

44.

84

29.

54

28.

71

28.

25

12.

94

11.

74

11.

60

11.

57

11.

10

10.

94

10.

80

10.

73

10.

68

10.

63

10.

55

ppm (t1)9.010.011.012.013.0

12

.94

11

.74

11

.60

11

.57

11

.10

10

.94

10

.80

10

.73

10

.68

10

.63

10

.55

13C NMR (C6D6, 100 MHz)

2

Zr NMe2N

Zr

N

NMe2

Zr

N

NMe2

solvent

ppm (t2)3.003.504.00

125.0

126.0

127.0

128.0

129.0

130.0

131.0

132.0

ppm (t1

ppm (t2)2.7002.7502.8002.8502.9002.9503.000

43.0

44.0

45.0

46.0

47.0

48.0

49.0ppm (t1

ppm (t2)3.504.004.50

57.0

58.0

59.0

60.0

61.0

62.0

ppm (t1

ppm (t2)1.9001.9502.0002.0502.1002.150

115.0

120.0

ppm (t1

HMQC of 2 (C6D6, 400 MHz) HMBC of 2 (C6D6, 400 MHz)

S33

1H NMR (C6D6, 400 MHz)

ppm (t1)0.01.02.03.04.05.06.07.08.0

1.9

50

.82

2.2

3

0.8

11

.00

0.8

4

6.5

9

1.1

7

1.0

5

14

.18

1.2

42

.84

30

.74

5.8

62

.71

2.5

32

.70

4.9

81

.00

12

.61

7.2

56

.00

2.0

3

19

.48

11

.48

ppm (t1)0.501.00

1.2

80

1.2

63

1.2

45

1.2

27

1.2

09

1.1

90

1.0

74

1.0

55

1.0

37

1.0

28

1.0

09

0.9

91

0.9

65

0.9

48

0.9

30

0.9

12

0.7

97

0.7

78

0.7

60

0.3

85

0.3

73

0.3

65

0.3

50

12

.61

7.2

5

6.0

0

19

.48

11

.48

Zr NH

Zr

N Zr

NH

NH

NH

NH

N

3a

solvent

standard (□)n-PrNH2 (▲)

1H NMR of 3a (C6D6, 400 MHz)

ppm (t1)2.503.003.504.004.50

4.5

23

4.4

99

4.4

82

4.4

05

4.3

93

4.3

76

4.3

64

4.1

16

4.0

85

4.0

58

3.9

93

3.9

78

3.9

61

3.9

46

3.9

29

3.9

14

3.8

56

3.8

41

3.8

25

3.8

11

3.7

94

3.7

79

3.6

09

3.5

93

3.5

79

3.4

84

3.4

66

3.4

33

3.3

41

3.3

23

3.3

10

3.2

91

3.2

77

2.8

53

2.8

36

2.5

96

2.5

74

2.3

58

2.3

46

2.3

25

2.3

12

1.9

5

0.8

2

2.2

1

0.8

1

1.0

0

0.8

4

6.5

9

1.1

7

14

.1

1.2

4

2.0

3

ppm (t1)1.9001.9502.0002.0502.1002.1502.2002.250

2.2

70

2.2

01

2.1

88

2.1

86

2.1

74

2.1

53

2.1

43

2.0

11

1.9

45

1.9

07

1.8

82

2.8

4

5.8

6

2.7

1

2.5

3

2.7

0

32

.76

Me2NH

S34

COSY of 3a (C6D6, 400 MHz)

ppm (t2)0.501.001.502.002.503.003.504.004.50

0.50

1.00

1.50

2.00

2.50

3.00

3.50

4.00

4.50ppm (t1

S35

ppm (t1)050100150

12

9.5

3

12

2.1

91

22

.02

11

8.1

81

17

.87

11

7.4

71

17

.41

11

6.5

31

16

.34

11

6.0

2

11

5.1

01

14

.86

11

4.3

5

11

3.7

1

62

.99

60

.01

59

.68

55

.82

55

.62

54

.62

54

.38

31

.42

31

.24

30

.60

30

.34

29

.98

29

.41

28

.82

13

.27

13

.11

12

.98

12

.82

12

.56

12

.32

12

.23

12

.14

12

.00

11

.75

11

.49

11

44

10

51

13C NMR (C6D6, 100 MHz)

ppm (t1)29.0029.5030.0030.5031.0031.50

31

.42

31

.24

30

.60

30

.34

29

.98

29

.41

28

.82

Zr NH

Zr

N Zr

NH

NH

NH

NH

N

3a

solvent

standard (□)n-PrNH2 (▲)

Me2NH

ppm (t1)114.0115.0116.0117.0118.0119.0120.0121.0122.0

12

2.1

9

12

2.0

2

11

8.1

8

11

7.8

7

11

7.4

7

11

7.4

1

11

6.5

31

16

.34

11

6.0

2

11

5.1

0

11

4.8

6

11

4.3

5

11

3.7

1

ppm (t1)10.5011.0011.5012.0012.5013.00

13.

27

13.

11

12.

98

12.

82

12.

56

12.

32

12.

23

12.

14

12.

00

11.

75

11.

49

11.

44

11.

37

11.

33

11.

28

10.

51

13C NMR of 3a (C6D6, 100 MHz)

S36

ppm (t1)0.01.02.03.04.05.06.07.08.0

1.0

01

.04

2.1

2

1.0

4

0.9

30

.91

5.4

9

1.1

11

.06

1.1

72

.11

1.3

21

.06

19

.16

2.9

1

0.9

71

.15

7.9

4

5.7

56

.07

2.4

92

.97

3.0

16

.09

ppm (t1)0.9000.9501.0001.0501.100

1.1

08

1.1

05

1.0

91

1.0

88

1.0

28

1.0

18

1.0

11

1.0

02

0.9

63

0.9

46

0.9

19

0.9

02

5.7

5

6.0

7

2.4

9

2.9

7

ppm (t1)4.504.604.704.804.905.005.10

5.0

08

4.9

90

4.9

79

4.9

61

4.8

98

4.8

81

4.8

70

4.8

53

4.8

42

4.8

25

4.5

68

4.5

57

4.5

27

4.5

17

1.0

0

1.0

4

2.1

2

1H NMR (C6D6, 400 MHz)

Zr NH

Zr

N Zr

N

NH

N

NH

4c

solvent

ppm (t1)2.503.003.50

3.7

60

3.7

46

3.7

27

3.7

13

3.6

91

3.6

72

3.6

53

3.5

21

3.5

01

3.4

84

3.4

22

3.4

10

3.3

89

3.3

77

3.3

41

3.3

20

3.2

75

3.1

69

3.1

51

3.1

34

3.1

20

3.1

02

3.0

61

3.0

47

3.0

31

3.0

14

3.0

00

2.5

75

2.5

54

2.5

40

2.5

23

2.5

08

2.4

91

2.4

76

2.4

63

1.0

4

0.9

3

0.9

1

5.4

9

1.1

1

1.0

6

1.1

7

2.1

1

1.3

2

1.0

6

ppm (t1)1.701.801.902.002.102.202.30

2.2

65

2.1

97

2.1

83

2.1

70

2.1

27

2.1

20

2.0

72

2.0

64

2.0

29

1.9

29

1.8

15

1.6

88

19

.16

2.9

1

7.9

4

3.0

1

6.0

9

ppm (t1)1.3501.4001.4501.5001.550

1.5

72

1.5

56

1.5

39

1.5

23

1.5

07

1.4

91

1.4

75

1.4

23

1.4

08

1.3

90

1.3

74

0.9

7

1.1

5

1H NMR of 4c (C6D6, 400 MHz)

S37

ppm (f2)2.503.003.504.004.505.00

2.50

3.00

3.50

4.00

4.50

5.00ppm (f1)

COSY of 4c (C6D6, 400 MHz)

S38

ppm (t1)050100150

13

3.7

1

12

5.2

4

12

4.1

6

11

9.5

11

19

.41

11

7.8

6

11

7.0

3

11

6.4

21

16

.36

11

5.5

7

11

5.0

41

14

.91

11

4.6

8

11

4.0

0

11

2.8

2

72

.05

66

.48

65

.73

60

.57

59

.34

55

.92

34

.31

34

.15

33

.83

32

.13

29

.35

29

.09

21

.54

21

.10

20

.97

20

.84

12

.09

12

.00

11

.83

11

.75

11

.74

11

.68

11

.60

11

.45

11

22

10

88

10

46

ppm (t1)112.0113.0114.0115.0116.0117.0118.0119.0

11

9.5

1

11

9.4

11

17

.86

11

7.0

3

11

6.4

21

16

.36

11

5.5

7

11

5.0

4

11

4.9

1

11

4.6

81

14

.00

11

2.8

2

Zr NH

Zr

N Zr

N

NH

N

NH

4c

13C NMR (C6D6, 100 MHz)solvent

ppm (t1)28.029.030.031.032.033.034.035.0

34

.31

34

.15

33

.83

32

.13

29

.35

29

.09

ppm (t1)21.0021.50

21.

54

21.

10

20.

97

20.

84

ppm (t1)10.5011.0011.5012.00

12.

09

12.

00

11.

83

11.

75

11.

74

11.

68

11.

60

11.

45

11.

22

10.

93

10.

88

10.

46

13C NMR of 4c (C6D6, 100 MHz)

S39

HMBC of 4c (C6D6)

ppm (f2)1.701.801.902.002.102.202.30

115.0

120.0

125.0

130.0

135.0

ppm (f1

ppm (f2)1.001.502.002.503.003.50

55.0

60.0

65.0

70.0

ppm (f1

ppm (f2)0.9000.9501.0001.0501.1001.150

32.50

33.00

33.50

34.00

34.50

35.00

35.50

36.00ppm (f1

S40

ppm (t1)0.01.02.03.04.05.06.07.08.0

1.5

20

1.4

90

0.8

54

1.0

0

1.0

32

.09

2.0

4

1.0

31

0.1

9

1.0

5

6.1

12

.89

2.8

92

.87

3.3

52

.71

2.7

15

.65

5.6

3

0.9

8

8.5

2

ppm (t1)2.402.502.602.702.802.903.00

2.9

51

2.9

33

2.9

22

2.8

14

2.7

77

2.7

08

2.6

89

2.4

59

2.4

54

2.4

39

1.0

3

10

.19

1.0

5

Zr N

Zr

N Zr

N

NMe2

N

5

1H NMR (C6D6, 400 MHz)

solvent

ppm (t1)4.404.504.604.704.804.905.005.10

5.0

79

4.9

62

4.9

46

4.9

31

4.9

14

4.7

97

4.4

24

4.4

06

4.3

92

4.3

74

1.0

0

1.0

3

2.0

9

2.0

4

ppm (t1)1.9001.9502.0002.0502.1002.1502.200

2.2

35

2.2

28

2.1

94

2.1

74

2.1

57

2.1

00

2.0

27

2.0

19

1.9

81

1.9

20

1.9

10

1.8

74

6.1

1

2.8

9

2.8

9

2.8

7

3.3

5

2.7

1

2.7

1

5.6

5

5.6

3

1H NMR of 5 (C6D6, 400 MHz)

S41

COSY of 5 (C6D6, 400 MHz)

ppm (f2)1.502.002.503.003.504.004.505.00

1.50

2.00

2.50

3.00

3.50

4.00

4.50

5.00ppm (f1

S42

ppm (t1)050100150

13

2.4

01

13

0.1

69

12

8.8

31

12

2.6

49

12

1.2

38

12

0.8

31

11

9.7

66

11

8.9

32

11

6.3

37

11

5.2

69

11

4.8

96

11

4.0

11

11

3.8

60

11

3.4

17

70

.495

67

.739

63

.660

62

.428

45

.158

33

.816

31

.155

30

.072

29

.398

28

.311

12

.677

12

.286

11

.847

11

.654

11

.312

11

.266

11

.156

11

.132

10

.969

10

.894

10

.879

10

.528

ppm (t1)

9.5010.0010.5011.0011.5012.0012.5013.00

12.

67

7

12.

28

6

11.

84

71

1.6

54

11.

31

21

1.2

66

11.

15

61

1.1

32

10.

96

9

10.

89

41

0.8

79

10.

52

8

13C NMR (C6D6, 100 MHz)

Zr N

Zr

N Zr

N

NMe2

N

5

solvent

ppm (t1)10.5011.0011.5012.0012.50

12

.67

7

12

.28

6

11

.84

7

11

.65

4

11

.31

21

1.2

66

11

.15

61

1.1

32

10

.96

9

10

.89

4

10

.87

9

10

.52

8

13C NMR of 5 (C6D6, 100 MHz)

S43

ppm (f2)4.404.504.604.704.804.905.005.10

65.0

70.0

ppm (f1

ppm (f2)1.502.00

60.0

61.0

62.0

63.0

64.0

65.0

66.0ppm (f1

ppm (f2)2.402.502.602.702.802.903.00

65.0

70.0

ppm (f1

HMQC of 5 (C6D6) HMBC of 5 (C6D6)

ppm (f2)1.902.002.102.202.30

115.0

120.0

125.0

130.0

ppm (f1

S44

ppm (f1)0.05.0

1.0

1

2.0

0

0.9

22

.97

2.0

40

.97

2.0

20

.92

2.0

3

1.0

1

1.0

0

1.0

2

0.9

20

.80

2.9

9

2.9

32

.66

3.1

30

.75

2.9

22

.95

6.5

55

.89

0.6

62

.92

1.7

72

.87

0.5

7

0.9

8

ppm (f1)0.05.0

1.0

1

2.0

0

0.9

22

.97

2.0

40

.97

2.0

20

.92

2.0

3

1.0

1

1.0

0

1.0

2

0.9

20

.80

2.9

9

2.9

32

.66

3.1

30

.75

2.9

22

.95

6.5

55

.89

0.6

62

.92

1.7

72

.87

0.5

7

0.9

8

ppm (f1)0.4500.5000.550

0.5

36

0.5

12

0.4

83

0.9

8

ppm (f1)6.507.007.50

7.4

82

7.4

64

7.3

65

7.3

44

6.9

94

6.9

74

6.8

29

6.8

13

6.4

55

6.4

34

6.2

77

6.2

57

6.1

95

6.1

73

0.9

2

2.9

7

2.0

4

0.9

7

2.0

2

0.9

2

2.0

3

1H NMR (C6D6, 400 MHz)

solvent

pentane

ppm (f1)2.503.003.504.004.505.00

5.1

83

5.1

64

5.1

45

5.1

26

5.1

03

4.4

70

4.4

50

4.4

39

4.4

14

4.0

08

3.9

92

3.9

82

3.9

66

3.3

75

3.3

57

3.3

39

3.3

22

3.3

03

2.8

14

2.7

99

2.7

79

2.7

64

2.7

28

2.7

07

2.6

86

2.5

87

2.5

74

2.5

69

2.5

40

1.0

1

2.0

0

1.0

1

1.0

0

1.0

2

0.9

2

0.8

0

ppm (f1)1.401.501.601.701.801.902.002.102.202.30

2.2

81

2.2

14

2.1

58

2.0

87

1.9

47

1.8

35

1.7

88

1.7

27

1.7

18

1.6

82

1.6

21

1.5

79

1.5

09

1.3

97

2.9

9

2.9

3

2.6

6

3.1

3

0.7

5

2.9

2

2.9

5

6.5

5

5.8

9

0.6

6

2.9

2

1.7

7

2.8

7

1H NMR of 6b (C6D6, 400 MHz)

toluene

S45

ppm (f2)6.507.007.50

6.50

7.00

7.50

ppm (f1

ppm (f2)2.002.503.003.504.004.505.00

2.00

2.50

3.00

3.50

4.00

4.50

5.00

ppm (f1

ppm (f2)0.501.001.50

0.50

1.00

1.50

ppm (f1

COSY of 6b (C6D6, 400 MHz)

ppm (f1)050100150

15

9.2

2

15

8.0

81

54

.68

13

5.1

41

31

.66

13

1.4

61

31

.06

13

0.9

3

12

6.1

51

26

.06

12

5.9

8

12

3.1

3

12

2.1

31

21

.92

12

0.7

71

20

.64

12

0.4

51

20

.21

11

9.6

3

11

8.7

91

18

.77

11

7.8

61

16

.01

11

5.8

11

13

.83

11

2.0

91

10

.19

11

0.1

41

06

.94

71

.55

51

.35

44

.42

30

.11

28

.25

23

.88

14

.42

13

.26

12

.43

12

.03

11

.81

11

.70

11

.50

10

.94

10

.84

10

.76

9.9

89

.82

13C{1H} NMR (C6D6, 400 MHz)solvent

Zr N

Zr

N Zr

N

N

NH

Br

Br

Br

NH2

6b

S46

ppm (f2)6.507.007.50

120.0

125.0

130.0

ppm (f1

ppm (f2)1.401.501.601.701.801.902.002.102.202.30

9.0

10.0

11.0

12.0

13.0

14.0

15.0ppm (f1

ppm (f2)2.03.04.05.0

45.0

50.0

55.0

60.0

65.0

70.0

75.0ppm (f1

ppm (f2)0.501.001.502.002.503.00

24.0

25.0

26.0

27.0

28.0

29.0

30.0

31.0ppm (f1

HSQC of 6b (C6D6)

HMBC of 6b (C6D6)

ppm (f2)5.506.006.507.007.50

110

120

130

140

150

160ppm (f1

ppm (f2)2.503.003.504.004.50

120.0

125.0

130.0

135.0

ppm (f1

ppm (f2)1.401.501.601.701.801.902.002.102.202.30

115.0

120.0

125.0

130.0

135.0

ppm (f1

ppm (f2)1.502.002.503.00

45.0

50.0

55.0

60.0

65.0

70.0

ppm (f1

S47

1H NMR (C6D6, 400 MHz)

ppm (t1)0.05.0

3.0

67

2.6

80

1.6

36

1.5

30

0.9

91

.00

1.9

7

0.9

7

2.9

9

5.7

80

.98

1.0

87

.32

1.7

11

.04

8.8

68

.62

3.0

93

.21

3.0

86

.00

8.7

88

.86

1.0

5

3.0

4

ppm (t1)6.806.907.007.107.207.307.40

7.3

38

7.3

33

7.3

18

7.3

13

7.2

78

7.2

74

7.2

59

7.2

55

6.8

32

6.8

13

6.7

93

0.9

9

1.0

0

1.0

5

solvent

ppm (t1)4.404.504.604.704.804.905.005.10

5.0

65

5.0

51

5.0

35

5.0

20

5.0

04

4.9

91

4.9

61

4.9

47

4.9

31

4.9

24

4.9

19

4.9

03

4.8

93

4.8

72

4.6

96

4.6

78

4.6

66

4.6

48

4.6

32

4.6

22

4.6

12

4.6

01

4.5

92

4.5

81

4.4

36

4.4

17

4.4

04

4.3

86

1.9

7

0.9

7

2.9

9

ppm (t1)1.801.902.002.102.202.30

2.3

11

2.2

59

2.2

41

2.0

49

1.9

72

1.9

68

1.9

41

1.9

31

1.8

65

1.8

08

3.0

9

3.2

1

3.0

8

6.0

0

8.7

8

8.8

6

3.0

4

1H NMR of 7 (C6D6, 400 MHz)

S48

ppm (f2)2.503.003.504.004.505.00

2.50

3.00

3.50

4.00

4.50

5.00

ppm (f1

COSY of 7 (C6D6, 400 MHz)

ppm (t1)050100150

16

3.1

1

13

8.1

9

13

6.8

9

13

0.0

4

12

8.5

6

12

5.5

3

12

5.0

6

12

4.3

8

12

2.0

5

12

1.6

21

21

.34

11

9.6

01

19

.45

11

7.8

2

11

6.3

41

16

.16

11

5.6

71

15

.28

67

.33

66

.96

61

.03

50

.26

49

.60

37

.13

35

.81

35

.78

32

.39

29

.82

29

.66

29

.39

14

.29

13

.77

12

.91

12

.68

12

.22

11

.98

11

.89

11

.73

11

.55

11

.20

10

.54

10

.00

13C NMR (C6D6, 100 MHz)solvent

S49

ppm (t2)1.801.902.002.102.202.30

115.0

120.0

125.0

130.0

ppm (t1

ppm (t2)2.502.602.702.802.903.003.103.203.30

48.00

48.50

49.00

49.50

50.00

50.50

51.00

51.50

ppm (t1

ppm (t2)1.5001.5501.6001.6501.700

135.50

136.00

136.50

137.00

137.50

138.00

138.50

139.00

139.50ppm (t1

ppm (t2)1.5001.5501.6001.650

32.0

33.0

34.0

35.0

36.0

37.0

38.0

ppm (t1

HMBC of 7 (C6D6)

S50

ppm (f1)0.01.02.03.04.05.06.07.08.0

2.1

50

1.9

71

1.4

24

0.9

04

0.6

42

1.8

8

2.1

02

.09

6.1

55

.89

9.0

0

17

.80

5.9

3

ppm (f1)3.103.203.303.40

3.4

15

3.3

96

3.3

78

3.2

26

3.2

02

3.1

95

3.1

71

3.1

04

3.0

85

3.0

73

3.0

54

1.8

8

2.1

0

2.0

9

1H NMR (C6D6, 400 MHz)

solvent

ppm (f1)050100150

12

7.5

1

12

4.6

8

10

0.2

7

62

.23

54

.77

35

.15

33

.60

27

.47

13

.94

11

.35

7.7

0

solvent

13C NMR (C6D6, 100 MHz)

Si

NZr

HN

NH

10

S51

ppm (t1)0.05.0

4.9

27

4.8

69

4.5

22

4.4

46

3.3

12

3.2

78

2.8

05

2.7

92

2.7

87

2.7

73

1.1

62

1.1

45

1.1

27

0.9

19

0.9

01

0.8

83

1.0

0

1.9

3

0.8

6

0.9

6

5.0

4

2.7

1

0.9

3

0.9

00

.99

3.1

0

2.8

1

2.7

52

.93

3.0

13

.20

2.9

65

.86

2.7

52

.89

3.0

62

.91

ppm (t1)1.801.902.002.102.202.302.40

2.4

44

2.3

29

2.2

63

2.2

22

2.1

84

2.1

29

2.0

30

1.9

45

1.9

27

1.8

17

1.7

97

2.7

1

2.7

5

2.9

33

.01

3.2

02

.96

5.8

6

2.7

52

.89

3.0

62

.91

ppm (t1)-2.200

-2.1

75

-2.1

85

-2.2

10

-2.2

18

0.9

3

ppm (t1)5.3505.4005.450

5.4

14

5.3

94

5.3

82

5.3

64

1.0

0

12a(+ 12a)

N

Zr NH

Zr

N Zr

N

NH

solvent

1H NMR (C6D6, 400 MHz)

ppm (f2)-2.0-1.00.01.02.03.04.05.0

-2.0

-1.0

0.0

1.0

2.0

3.0

4.0

5.0

ppm (f1

COSY of 12a (C6D6, 400 MHz)

S52

ppm (t1)050100150

13

2.2

21

30

.43

11

9.0

41

18

.90

11

8.5

61

18

.36

11

6.7

11

16

.29

11

4.8

31

14

.72

11

4.2

81

14

.21

11

4.1

31

13

.86

91

.23

72

.13

65

.09

55

.62

52

.64

38

.60

32

.48

31

.35

30

.70

30

.28

19

.53

ppm (t1)9.010.011.012.013.0

13

.02

12

.52

12

.06

11

.65

11

.56

11

.14

10

.97

10

.88

10

.76

10

.44

10

.40

9.9

9

12a(+ 12a)

N

Zr NH

Zr

N Zr

N

NH

solvent

13C NMR (C6D6, 100 MHz)

ppm (f2)2.503.003.504.004.505.005.50

55.0

60.0

65.0

70.0

ppm (f1

ppm (f2)2.0002.0502.1002.1502.2002.2502.300

89.50

90.00

90.50

91.00

91.50

92.00

92.50

93.00

ppm (f1

HSQC of 12a (C6D6) HMBC of 12a (C6D6)

ppm (t2)0.800.901.001.101.20

30

40

50

60

70

80

90

ppm (t1

ppm (t2)2.002.50

115.0

120.0

125.0

130.0

ppm (t1

S53

ppm (f1)0.01.02.03.04.05.06.07.08.0

2.7

87

2.7

70

2.7

53

2.2

08

2.1

91

2.1

73

1.6

19

1.6

02

1.5

85

1.5

68

1.5

50

1.1

71

1.9

6

2.0

0

2.0

0

11

.37

solvent

1H NMR (CDCl3, 400 MHz)

ppm (f1)050100150

89

.43

77

.69

41

.30

32

.88

31

.34

27

.31

16

.13

solvent

13C NMR (CDCl3, 100 MHz)

S54

1H NMR (CDCl3, 400 MHz)

ppm (f1)0.01.02.03.04.05.06.07.08.0

2.5

26

1.1

28

1.1

10

1.0

91

0.9

08

5.9

9

3.0

2

2.0

01

.89

1.9

4

ppm (f1)2.0502.1002.1502.200

2.1

89

2.1

83

2.1

76

2.1

70

2.1

64

2.1

58

2.1

51

2.1

45

2.1

39

2.1

33

2.1

27

2.1

21

2.0

45

2.0

39

2.0

33

2.0

0

1.8

9

solvent

S55

N

Bu-t

15c

ppm (f1)0.01.02.03.04.05.06.07.08.0

1.0

13

1.9

0

2.0

02

.05

8.9

4

2.1

2

ppm (f1)3.7003.7503.800

3.7

94

3.7

90

3.7

86

3.7

82

3.7

78

3.7

71

3.7

68

3.7

65

3.7

58

3.7

54

3.7

50

3.7

46

3.7

42

1.9

0

ppm (f1)1.450

1.4

80

1.4

62

1.4

40

1.4

23

1.4

03

2.1

2

ppm (f1)2.0502.1002.150

2.1

45

2.0

94

2.0

87

2.0

83

2.0

68

2.0

51

2.0

47

2.0

42

2.0

0

2.0

5

standard (□)13c (▲)

solvent

1H NMR (C6D6, 400 MHz)

solvent

13C NMR (C6D6, 100 MHz)

N

Bu-t

15c

standard (□)13c (▲)

ppm (t1)050100150

17

4.9

3

61

.55

46

.94

40

.15

31

.29

30

.17

23

.07

S56

ppm (f1)0.05.0

1.9

25

2.0

0

2.0

42

.04

2.0

1

8.8

5

ppm (f1)0.8700.8800.8900.900

0.9

05

0.8

86

0.8

74

0.8

68

8.8

5

ppm (f1)1.5501.600

1.6

29

1.6

11

1.5

92

1.5

74

1.5

55

1.5

37

2.0

1

ppm (f1)2.0902.1002.1102.1202.1302.140

2.1

33

2.1

15

2.0

96

2.0

4

ppm (f1)3.550

3.5

58

3.5

54

3.5

50

3.5

46

3.5

42

2.0

0

standard (□)

solvent

1H NMR (C6D6, 400 MHz)

solvent

13C NMR (C6D6, 100 MHz)

standard (□)

ppm (f1)050100150

17

5.7

7

74

.78

52

.38

38

.28

36

.34

28

.02

19

.90

14

.21

S57

ppm (t1)0.01.02.03.04.05.06.07.08.0

1.1

60

.89

0.9

10

.95

1.8

91

.00

5.3

22

.16

1.9

2

1.8

5

6.1

8

1.1

00

.99

1.1

5

7.8

08

.51

17

.65

3.0

53

.07

3.2

02

.98

6.7

02

.63

4.5

42

0.5

32

.99

2.9

95

.08

2.7

5

ppm (t1)0.300.400.500.600.700.80

0.8

72

0.7

55

0.7

39

0.7

23

0.7

08

0.3

40

0.3

21

0.3

06

1.1

0

0.9

9

1.1

5

ppm (t1)1.2801.2901.3001.310

1.3

12

1.3

04

1.2

86

1.2

82

7.8

0

8.5

1

17

.65

1H NMR (C6D6, 400 MHz)

solvent

13c (□)standard (▲)

Zr NH

Zr

N Zr

NH

NH

NH

NH

N

Bu-t

Bu-t

t-Bu

t-Bu

17c

ppm (t1)3.003.504.004.50

4.4

73

4.4

58

4.4

42

4.4

27

4.3

86

4.3

67

4.3

46

4.2

69

4.2

58

4.2

39

4.2

28

4.1

09

4.0

78

4.0

47

3.9

89

3.9

72

3.9

57

3.9

41

3.9

25

3.9

12

3.8

06

3.5

56

3.3

74

2.9

33

1.1

6

0.8

9

0.9

1

0.9

5

1.8

9

1.0

0

5.3

2

2.1

6

1.9

2

ppm (t1)1.902.002.102.202.30

2.2

86

2.2

28

2.2

02

2.1

64

2.1

51

2.1

40

2.1

02

2.0

52

1.9

62

1.9

08

1.8

71

3.0

5

3.0

7

3.2

0

2.9

8

6.7

0

4.5

4

20

.53

2.9

9

2.9

9

5.0

8

2.7

5

1H NMR of 17c (C6D6, 400 MHz)

S58

ppm (t2)0.501.001.502.002.503.003.504.004.50

0.50

1.00

1.50

2.00

2.50

3.00

3.50

4.00

4.50ppm (t1

COSY of 17c (C6D6, 400 MHz)

S59

13C NMR (C6D6, 100 MHz)

ppm (t1)050100150

12

9.6

8

12

8.7

5

12

2.4

41

22

.17

11

8.4

61

18

.12

11

7.7

41

17

.69

11

6.7

11

16

.44

11

6.1

6

11

5.4

01

14

.95

11

4.4

9

11

3.8

38

9.4

58

9.0

48

8.8

48

8.7

8

79

.62

79

.24

78

.88

77

.95

63

.08

60

.16

57

.50

55

.70

53

.02

51

.81

51

.25

36

.40

36

.37

36

.27

35

.75

31

.83

31

.81

31

.79

31

.71

31

.38

31

.18

28

.74

27

.72

27

.63

18

.74

18

.02

17

.15

17

.07

13

.25

13

.22

12

45

12

03

12

00

11

88

11

71

11

57

solvent

13c (□)standard (▲)

ppm (t1)115.0120.0

12

2.4

4

12

2.1

7

11

8.4

6

11

8.1

2

11

7.7

4

11

7.6

9

11

6.7

1

11

6.4

4

11

6.1

6

11

5.4

0

11

4.9

5

11

4.4

9

11

3.8

3

ppm (t1)11.012.013.014.015.016.017.018.019.0

18

.74

18

.02

17

.15

17

.07

13

.25

13

.22

12

.45

12

.03

12

.00

11

.88

11

.71

11

.57

11

.39

11

.29

10

.85

13C NMR of 17c (C6D6, 100 MHz)

S60

ppm (t1)0.05.0

1.2

81

1.2

71

0.9

8

0.9

61

.28

1.0

2

1.0

9

0.8

8

4.3

3

4.1

53

2.8

2

1.1

11

.05

1.0

0

7.0

03

6.1

8

2.9

92

.53

2.2

42

.76

5.1

1

ppm (t1)-2.250-2.200-2.150

-2.1

89

-2.2

14

1.0

0

ppm (t1)0.300.400.500.60

0.5

89

0.5

67

0.3

85

0.3

63

1.1

1

1.0

5

1H NMR (C6D6, 400 MHz)

solvent

ppm (t1)3.003.504.004.505.005.50

5.3

67

5.3

47

5.3

35

5.3

15

4.9

51

4.9

36

4.9

20

4.9

03

4.8

90

4.8

59

4.8

41

4.8

31

4.8

15

4.8

00

4.7

84

4.4

38

4.4

19

4.4

02

4.3

87

4.3

68

3.2

93

3.2

73

3.2

67

3.2

60

3.2

47

3.2

39

3.2

34

3.2

14

3.0

08

2.9

89

2.7

65

0.9

8

0.9

6

1.2

8

1.0

2

1.0

9

0.8

8

4.3

3

ppm (t1)1.801.902.002.102.202.302.402.50

2.4

18

2.2

69

2.2

56

2.2

26

2.2

17

2.0

99

2.0

25

1.9

42

1.9

03

1.8

48

1.8

14

7.0

0

36

.18

2.9

9

2.5

3

2.2

4

2.7

6

5.1

1

1H NMR of 18c (C6D6, 400 MHz)

S61

ppm (t1)050100150

13

2.1

8

13

0.6

1

12

6.6

7

89

.30

89

.02

87

.86

79

.89

79

.05

72

.30

65

.14

52

.66

45

.32

39

.10

31

.77

31

.73

27

.71

27

.69

17

.55

13C NMR (C6D6, 100 MHz)solvent

ppm (t1)114.0115.0116.0117.0118.0119.0

11

9.2

9

11

9.1

1

11

8.7

9

11

8.5

0

11

6.9

0

11

6.4

2

11

5.1

0

11

4.9

7

11

4.4

8

11

4.3

41

14

.30

11

4.1

5

ppm (t1)10.0010.5011.0011.5012.0012.5013.00

13

.03

12

.03

11

.58

11

.47

11

.40

11

.09

11

.08

11

.02

10

.98

10

.90

10

.45

10

.00

13C NMR of 18c (C6D6, 100 MHz)

S62

ppm (f2)2.002.503.003.504.004.505.005.50

50.0

55.0

60.0

65.0

70.0

75.0

ppm (f1

ppm (f2)1.902.002.102.202.302.402.50

85.50

86.00

86.50

87.00

87.50

88.00

88.50

ppm (f1

ppm (f2)2.002.503.003.504.004.505.00

126.0

127.0

128.0

129.0

130.0

131.0

132.0

133.0

ppm (f1

ppm (f2)1.801.902.002.102.202.302.40

114.0

115.0

116.0

117.0

118.0

119.0

120.0ppm (f1

HSQC of 18c (C6D6) HMBC of 18c (C6D6)

S63

1H NMR (C6D6, 400 MHz)

ppm (t1)0.05.0

2.8

92

2.7

37

4.0

9

5.2

03

.05

1.0

00

.98

0.8

70

.92

0.8

5

1.0

0

0.9

51

.67

5.7

3

2.7

42

.91

2.6

72

.84

2.5

52

.94

3.0

72

.64

2.7

45

.50

2.5

82

.57

2.6

3

4.2

2

6.7

3

ppm (t1)1.100

1.1

30

1.0

86

2.7

4

2.9

1

ppm (t1)3.1003.1503.2003.2503.300

3.2

83

3.2

56

3.1

64

3.1

37

1.0

0

0.9

8

complex 2 (□)16b (▲)

solvent

ppm (t1)4.004.505.00

5.2

54

4.8

72

4.8

53

4.8

48

4.8

40

4.8

30

4.8

18

4.7

97

4.5

48

4.5

34

4.5

17

4.5

03

4.4

88

4.4

74

4.3

84

4.3

68

4.3

53

4.3

36

4.2

90

4.0

27

3.8

92

0.8

7

0.9

2

0.8

5

1.0

0

0.9

5

1.6

7

ppm (t1)1.9001.9502.0002.0502.1002.150

2.1

34

2.0

91

2.0

78

2.0

42

2.0

37

1.9

89

1.9

72

1.9

59

1.9

50

1.9

36

1.9

18

1.8

87

2.6

7

2.8

4

2.5

5

2.9

4

3.0

7

2.6

4

2.7

4

5.5

0

2.5

8

2.5

7

2.6

3

1H NMR of 20b (C6D6, 400 MHz)

S64

ppm (t2)2.503.003.504.004.505.00

2.50

3.00

3.50

4.00

4.50

5.00

ppm (t1

COSY of 20b (C6D6, 400 MHz)

S65

13C NMR (C6D6, 100 MHz)

ppm (t1)050100150

16

0.7

7

14

2.9

7

13

0.5

6

12

9.0

41

28

.93

12

6.4

4

12

5.5

4

12

1.1

71

20

.77

12

0.5

21

20

.36

11

9.3

21

19

.00

11

8.7

6

11

7.6

01

15

.98

11

5.6

3

11

4.3

1

95

.53

66

.58

62

.81

61

.51

59

.25

48

.65

46

.30

46

.09

38

.74

29

.57

29

.40

28

.88

28

.60

28

.57

13

.06

12

.43

11

.92

11

.70

11

.66

11

.48

11

.14

11

.01

10

.68

10

.66

10

32

solvent

ppm (t1)115.0120.0125.0

12

6.4

4

12

5.5

4

12

1.1

7

12

0.7

7

12

0.5

2

12

0.3

6

11

9.3

2

11

9.0

01

18

.76

11

7.6

0

11

5.9

8

11

5.6

3

11

4.3

1

ppm (t1)10.5011.0011.5012.0012.5013.00

13

.06

12

.43

11

.92

11

.70

11

.66

11

.48

11

.14

11

.01

10

.68

10

.66

10

.32

13C NMR of 20b (C6D6, 100 MHz)

S66

ppm (t2)4.004.505.00

60.0

65.0

70.0

75.0

80.0

85.0

90.0

95.0

ppm (t1

ppm (t2)2.602.702.802.903.003.103.203.30

45.0

50.0

55.0

60.0

65.0

ppm (t1

ppm (t2)2.602.702.802.903.003.103.203.30

155.0

160.0

165.0

ppm (t1

ppm (t2)1.001.502.002.50

30

40

50

60

70ppm (t1

HSQC of 20b (C6D6) HMBC of 20b (C6D6)