1 Synthesis and Structural Characterization, of Nickel(II) Complexs Supported by...
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1 Synthesis and Structural Characteriz ation, of Nickel(II) Complexs Suppor ted by Aminodipyridylphosphine Oxide Ligand. The Catalytic Application to Thioace talization of Aldehyde 學學 學學學 ： 學學學學 學學學 學學 ： Thioacetalization HO N H P O N N Ni Br Br
1 Synthesis and Structural Characterization, of Nickel(II) Complexs Supported by Aminodipyridylphosphine Oxide Ligand. The Catalytic Application to Thioacetalization
1 Synthesis and Structural Characterization, of Nickel(II)
Complexs Supported by Aminodipyridylphosphine Oxide Ligand. The
Catalytic Application to Thioacetalization of Aldehyde
Thioacetalization
Slide 2
2 Corey-Seebach Reaction Seebach, D.; Jones, N. R.; Corey, E.
J. J. Org. Chem. 1968, 33, 300-105. n=2-6 Base
Slide 3
3 Acetalization and Thioacetalization of Carbonyl
Compounds
Slide 4
4 The Earlier Catalyst for Thioacetalization J.W. Ralls, et.
al., J. Am.Chem. Soc. 1949, 71, 3320-3325
Slide 5
5 HCl Catalyzed Thioacetalization Robert Ramage, et. al., J.
Chem. Soc., Perkin Trans. 1 1984, 71, 1547-1553.
Slide 6
6 Lewis Acid Catalyzed Thioacetalization Conventional Lewis
Acids BF 3 -Et 2 O ZnCl 2 AlCl 3 SiCl 4 LiOTf InCl 3 Nakata, T. et.
al., Tetrahedron Lett. 1985, 26, 6461-6464. Evans, D. V. et. al.,
J. Am. Chem. Soc. 1977, 99, 5009-5017. Firouzabadi, H. et. al.,
Bull. Chem. Soc. Jpn. 2001, 74, 2401-2406. Transition Metal Lewis
Acids TiCl 4 WCl 6 CoCl 2 Sc(OTf) 3 MoCl 5 NiCl 2 Kumar, V. et.
al., Tetrahedron Lett. 1983, 24, 1289-1292. Firouzabadi, H. et.,
al. Synlett 1998, 739-741. Goswami, S. et. al., Tetrahedron Lett.
2008, 49, 3092-3096. Lanthanide Metal Lewis Acids Lu(OTf) 3 Nd(OTf)
3 Kanta, D. S. J. Chem. Res. Synop. 2004,230-231. Kanta, D. S.
Synth. Commun. 2004, 34, 230-231.
Slide 7
7 BF 3 -Et 2 O Catalyzed Thioacetalization One use only Paulo
J.S. Moran. J. Organomet. Chem., 2000, 603, 220-224
Slide 8
8 MoCl 5 or MoO 2 Cl 2 Catalyzed Thioacetalization S. Goswami,
A. C. Maity. Tetrahedron Letters, 2008, 49, 30923096 One use
only
Slide 9
9 CoCl 2 Catalyzed Thioacetalization 1hr 91 % One use only 5
mole% CoCl 2 Surya Kanta De. Tetrahedron Letters, 2004, 45,
10351036
Slide 10
10 Nickel(II) Chloride Catalyzed Thioacetalization 2.5 hour 96
% A. T. Khan et al., Tetrahedron Lett. 2003, 44, 919922 One use
only 10 mole % NiCl 2
Slide 11
11 Motivation 1.Traditional high valent metal halide Lewis
acids are difficult to handle ex. MCl n,M=Zn W Co Mo.. 2.Nickel is
less expensive than other transition metal NiCl 2 50g $ 29.2 WCl 6
100g $ 152.5 PdCl 2 25g $ 849 NIBr 2 50g $ 72.2 W(CO) 6 50g $ 176
3.(DME)NiBr 2 as preferable precursor not (DME)NiCl 2 [HO(CH 2 ) 11
N(H)P(O)(2-py) 2 ]NiBr 2 & [HO(CH 2 ) 11 N(H)P(O)(2-py) 2 ]NiCl
2 4.Use HO(CH 2 ) 11 N(H)P(O)(2-py) 2 as chelate ligand [HO(CH 2 )
11 N(H)P(O)(2-py) 2 ]NiBr 2
Slide 12
12 Ni => small o => tetrahedral & square planar Pd
& Pt => large o => square planar Ligands => large,
weak-field => tetrahedral Ligands => small, strong-field
=> square planar Comparison of M 2+ (d 8 species) Square Planar
vs. Tetrahedral Complexes
Slide 13
13 R. G. Hayter, F. S. Humiec. Inorg. Chem. 1965, 12,
1701-1706. The tetrahedral structure is increasingly favored in the
orders PPh 2 R P(C 2 H 5 ) 3 < P(C 2 H 5 ) 2 C 6 H 5 < PC 2 H
5 (C 6 H 5 ) 2 < P(C 6 H 5 ) 3 X Cl < Br < I Square Planar
- Tetrahedral Isomerism of Nickel Halide Complexes of Ni(PPh 2 R) 2
X 2
16 Chemical Shift of Paramagnetic Compounds for NMR observed =
diamagnetic + hyperfine diamagnetic = diamagnetic shift corresponds
to the values for the free ligand. hyperfine = contact + dipolar
contact = contact shifts are caused by spin delocalization of the
unpaired electrons through chemical bonds (through bond) dipolar =
dipolar shifts, between the paramagnetic center and the nucleus of
interaction (through space) due to the paramagnetic center presence
Major Broad signal J. Phys. Chem. A, 2003, 107, 5821-5825
Slide 17
17 Square planar Tetrahedral
Slide 18
18 IR of [HO(CH 2 ) 11 N(H)P(O)(2-py) 2 ]NiBr 2 HO(CH 2 ) 11
N(H)P(O)(2-py) 2 1569 cm -1 1428 cm -1 1593 cm -1 1430 cm -1 [HO(CH
2 ) 11 N(H)P(O)(2-py) 2 ]NiBr 2
Slide 19
19 EPR of HO(CH 2 ) 11 N(H)P(O)(2-py) 2 ]NiBr 2 g=2 g =
2.18
Slide 20
20 SUQID of HO(CH 2 ) 11 N(H)P(O)(2-py) 2 ]NiBr 2 = m / H m = (
/ W) M eff = (3k / N2)1/2(mT)1/2 = 2.828( m T) 1/2 m , H (10000
guess), m , W , M eff , T , K , N 6.02 x 1023 slope = 1/( m T) =
0.936 m T = 1/0.936 eff = 2.828 ( m T) 1/2 eff = 2.92
Slide 21
21 HO(CH 2 ) 11 N(H)P(O)(2-py) 2 ]NiBr 2 Tetrahedral eff = 2.92
The Organometallic Chemistry of The Transition Metals. 2005
34 Near Future Work for Nickel(II) Complex Immobilization onto
AuNPs surfaces NiBr 2 (DME) Cat.
Slide 35
35 Conclusions 1.We have successfully synthesized an air- and
water-stable and efficient catalyst { [HO(CH 2 ) 11 NHPOpy 2 ]NiBr
2 }. 2. We use 1 H NMR FT-IR EPR SQUID and FAB-MS for structural
characterization of Nickel(II) complex, we have proved the compound
demonstrated that it is a paramagnetic tetrahedral compound, and we
will proceed detection of Elemental Analysis (EA). 3.In Ni-catalyst
series, the Nickel(II) complex only can be reused for catalytic of
thioacetalization of aldehyde many times without any loss of
reactivity.
Slide 36
36 Chemoselectivities in Acetalization, and Thioacetalization
J. Phys. Chem. A 2006, 110, 2181-2187
38 EPR of [Ni(CTH)DTBSQ]PF 6 at B = 3.2 Tesla g = 2 g 1 = 5.8 g
1 = 2.4 g 1 = 1.7 Inorganic Chemistry, 1988, 27, 2831-2836
Zero-field spectra and Kramers degeneracy (Kramers doublet)
