15308-54-0Relevant academic research and scientific papers
Reactions of CS2 with nickel-phosphine complexes: Structure of Ni(SC(S)SC(PMe3)S)(PMe3)
Mason, Michael G.,Swepston, Paul N.,Ibers, James A.
, p. 411 - 418 (2008/10/08)
The reactions of carbon disulfide with a number of nickel(0)-phosphine complexes (generated from Ni(COD)2 and added phosphine) afford two classes of Ni-CS2 coordination compounds. For L = PPh3, P(p-tol)3, and PCy3 compounds characterized as [Ni(CS2)L]2 are formed. The compounds Ni(C2S4PR3)(PR3) are produced when R = CH3 or C2H5, as deduced from spectroscopic and X-ray analysis. The complex Ni(SC(S)SC(PMe3)S)(PMe3) crystallizes in the orthorhombic space group D24-P212121 (a = 13.486 (3) ?, b = 13.500 (2) ?, c = 17.670 (3) ?) with two enantiomorphically related molecules per asymmetric unit. This crystal structure is a rare example of a racemic mixture crystallizing in an acentric space group. The final agreement indices, based on 271 variables and 6034 unique reflections collected at -151°C on an automatic diffractometer, are R(F2) = 0.051 and Rw(F2) = 0.082. The conventional R index on F for 5197 reflections having F02 > 3σ(F02) is 0.034. The complex displays a NiPSCS coordination (mean Ni-P 2.165 (7) ?; mean Ni-S 2.156(5) ?; mean Ni-C 1.92 (1) ?) that is severely distorted from square planar with a mean S-Ni-S angle of 138.9 (2)°, a mean C-Ni-P angle of 161.7 (2)°, mean C-Ni-S angles of 50.4 (3) and 92.9 (6)°, and deviations from the NiPSCS plane as large as 0.34 (3) ?. The SC(S)SC(PMe3)S linkage contains a planar SC(S)S fragment (largest deviation 0.026 (3) ?) and a nonplanar SC(P)S fragment (largest deviation 0.265 (6) ?). The bond length pattern found for this ligand (S-C range 1.662 (7)-1.793 (6) ?) is consistent with 13C{1H} NMR results that show that the carbon atom of the SC(S)S fragment is coupled to the metal-bound phosphine but not to the carbon-bound phosphine. This lack of coupling can be ascribed to a S-C single bond (S-C = 1.793 (6) ?) within the ligand that blocks communication between the phosphine and the carbon atom.
