112792-43-5Relevant articles and documents
Preparation and Properties of, and Reactions with, Metal-Containing Heterocycles, LIX. - Synthesis and Properties of η2-Thiophosphinito Complexes of Cobalt
Lindner, Ekkehard,Frick, Klaus Erich,Fawzi, Riad,Hiller, Wolfgang,Staengle, Michael
, p. 1075 - 1084 (2007/10/02)
The η2-thiophosphinito complexes (OC)2(R2R21P)Co(η2-PR23S) (3a, b, d, e, i, j, k, m, n) are obtained by reaction of ICo(CO)2(PR3)2 (1, 2) with the secondary phosphane sulfides R23HP=S in the presence of Et(iPr)2N.The Me2PS and Et2PS compounds 3a, b, d oligomerize easily to form 2R21P)Co(μ-PR23S)>n (4a, b, d) (n > 2).Upon exchange of PR21R2 (R1 = R2 = Ph) in 3a, d, j, m by PPh2Me, PPhMe2, and PMe3 in addition to the η2-thiophosphinito complexes 3f, g, l the dimeric species 2R21P)Co(μ-PR23S)>2 (5c, f, g, h, o) are formed.The dimerization tendency depends on the steric demand of the substituents R1, R2, and R3.The substituents R1 and R2 in 5f, g are responsible for energetically preferred rotamers, which are indicated in the 31P-NMR spectra.The barrier of rotation is calculated to give ΔG(excit.) = 42 kJ/mol.According to X-ray structural analysis (OC)2(Cy3P)Co(η2-PEt2S) (3e), S)>2 (5c), and S)>2 (5f) crystallize in the space group P21/c, P andP21/c with Z = 4, 2, and 2, respectively.
