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Unexpected formation of [Ru(η5-C5H5)(PH{CH2N(CH2CH2)2O}2)(PPh3)2]BF4 -
the first „piano-stool” ruthenium complex bearing secondary aminomethylphosphane ligand
Michał Płotek,a,b Radosław Starosta,c* Urszula K. Komarnicka,c Agnieszka Skórska-Stania,a Grażyna Stochel,a Agnieszka Kyzioła* and Małgorzata Jeżowska-Bojczukc
a Faculty of Chemistry, Jagiellonian University in Krakow, Ingardena 3, 30-060 Krakow, Polandb Faculty of Conservation and Restoration of Works of Art, Jan Matejko Academy of Fine Arts in Krakow, Lea 27-29, 30-052 Krakow, Polandc Faculty of Chemistry, University of Wroclaw, Joliot-Curie 14, 50-383 Wroclaw, Poland* corresponding authors: AK - [email protected]; RS- [email protected]
In this paper we report the reaction of [Ru(η5-C5H5)Cl(PPh3)2] with P{CH2N(CH2CH2)2O}3 in the presence of NaBF4, in which apart from the Clˉ substitution, an unexpected P-C bond cleavage in the tertiary phosphane is observed. It results in formation of the [Ru(η5-C5H5)(PH{CH2N(CH2CH2)2O}2)(PPh3)2]BF4 (1) – the first “piano-stool” ruthenium complex with secondary aminomethylphosphane ligand.
Fig. S1 Structure of complex 1 with atom numbering scheme.
Fig. S2 Comparison of the 31P and 31P{1H} NMR spectra (CDCl3, 300 K) of complex 1.
Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2014
Fig. S3 31P{1H} NMR spectra (CDCl3, 300 K) of reaction mixture (before puryfication and crystallization).
Fig. S4 1H NMR spectra (CDCl3, 300 K) of complex 1 (2.1 – 3.8 ppm region).
Fig. S5 1H NMR spectra (CDCl3, 300 K) of complex 1 (4.85 – 7.6 ppm region).
Fig. S6 13C{1H} NMR spectra (CDCl3, 300 K) of complex 1.
Fig. S7 1H NMR spectra (CDCl3, 300 K) of starting complex [Ru(η5-C5H5)Cl(PPh3)2].
Fig. S8 13C{1H} NMR spectra (CDCl3, 300 K) of starting complex [Ru(η5-C5H5)Cl(PPh3)2].
Table S1. Comparison of NMR data for complex 1, PPh3 and starting reagents: [Ru(η5-C5H5)Cl(PPh3)2], P(CH2-morph)3.P(CH2-morph)3 PPh3 [Ru(η5-C5H5)Cl(PPh3)2] 1
Atomic number σ [ppm] multiplicity J [Hz] σ [ppm] multiplicity
J [Hz] σ [ppm] multiplicity J [Hz] σ [ppm] multiplicity
J [Hz]1H NMR
H11 2.59 (2H) d 2J(H11-P1) = 2.1 - - - - 2.94 (4H) mH12 2.50 (4H) m - - - - 2.28 (8H) mH13 3.63 (4H) m - - - - 3.62 (8H) m
H1-H5 - - - - 4.12 (5H) s 4.95 (5H) sH32 - - - - 7.39 (12H) m 6.94 (12H) bt J = 8.6H33 - - - - 7.14 (12H) t J = 7.3 7.33 (12H) t J = 7.2H34 - - - - 7.24 (6H) t J = 7.3 7.45 (6H) t J = 7.2
13C{1H} NMRC11 55.80 d 1J(C1-P1) = 7.8 - - - - 55.97 d 1J(C11-P1) = 36.1C12 54.64 d 3J(C11-P1) = 8.3 - - - - 54.31 d 3J(C12-P1) = 5.5C13 66.45 s - - - - 66.95 s
C1-C5 - - - - 81.39 m 85.42 sC31 - - 137.14 d 1J(C31-P1) = 10.8 138.35 m 136.41 mC32 - - 133.71 d 2J(C32-P1) = 19.8 133.77 t J = 5.0 133.56 bt J = 4.8C33 - - 128.46 d 3J(C33-P1) = 7.1 127.45 t J = 4.5 128.52 bt J = 4.1C34 - - 128.68 s 128.66 s 130.42 s
31P{1H} NMRP1 -61.47 s -4.70 - - - -12.96 t 2J(P1-P2,3) = 41.2
P2, P3 - - - - 38.34 s 42.03 d 2J(P2,3-P1) = 41.231P NMR
P1 -61.47 s - - - - -12.96 d-t 2J(P1-P2,3) = 41.2 1J(P1-H1P) = 338.6
P2, P3 - - - - 38.34 s 42.03 d 2J(P2,3-P1) = 41.2s – singlet, d – doublet, t – triplet, m – multiplet, b - broad
Fig. S9 IR-ATR spectrum of complex 1.
Fig. S10 +ESI mass spectrum of complex 1 (MeOH).
Fig. S11 +ESI mass spectrum of complex 1 (MeOH/HCOOH).
Table S2 Crystal data for complex 1.
Parameters 1
Empirical formula C51H56BF4N2O2P3Ru
Formula weight (g∙mol-1) 1009.77
Temperature (K) 119.8(5)
Type of radiation Mo Kα (0,71073 Å)
Crystal system tetragonal
Space group I41/a
Crystal information
Description block
Colour yellow
Size [mm] 0.28×0.25×0.15
Unit cell dimensions
a (Å) 28.1859(1)
b (Å) 28.1859(1)
c (Å) 23.7177(2)
α (°) 90
β (°) 90
γ (°) 90
Volume (Å3) 18842.4(2)
Z 16
Density calculated (Mg/ m3) 1.424
Absorption coefficient (mm-1) 0.493
F(000) 8352
θmin – θmax (°) 2.86 to 27.50
hkl range
-35 ← h ← 36
-36 ← k ← 36
-30 ← l ← 30
Reflections collected 132166
Independent reflections 10782
Rint 0.0366
Completeness to θmax (%) 99.7
Absorption correction type Multi-scan
Tmax and Tmin 0.915,1.000
Data / restraints / parameters 10782 / 0 / 580
Goodness of fit F2 1.060
R1, wR2 [I>2σ(I)] R1 = 0.0287, wR2 = 0.0670
R1, wR2 (all data) R1 = 0.0374, wR2 = 0.0726
Largest diff. peak and hole (e Å-3) 1.008 and -0.427
Fig. S12 Crystal cell packing of 1 – view along a axis.
Fig. S13 Crystal cell packing of 1 – view along b axis.
Fig. S14 Crystal cell packing of 1 – view along c axis.
