83418-26-2Relevant articles and documents
Synthesis and Structural Characterisation of Mixed Bimetal Compounds containing Molybdenum
Otsuka, Sei,Okura, Nobuyuki,Payne, Nicholas C.
, p. 531 - 532 (1982)
Reaction of Mo(SBut)4 or Mo(SBut)2(CNBut)4 with CuBr(CNBut)3 or 'Pd(CNBut)2' gives mixed d4-d10 bimetal compounds; X-ray crystallographic studies have confirmed the presence of a highly delocalized MoS2Cu core in two conformational isomers of (ButNC)4Mo(μ-SBut)2CuBr.
Synthesis and X-ray Structures of the Conformational Isomers of the Mixed Bimetal Complex (t-BuNC)4Mo(μ-t-BuS)2CuBr
Payne, Nicholas C,,Okura, Noboyuki,Otsuka, Sei
, p. 245 - 251 (1983)
The molecular fragment cis-Mo(t-BuS)2 has been found to act as a bidentate ligand, exhibiting affinity toward d10 metals.Reaction of Mo(t-BuS)4 or cis-(Mo(t-BuS)2(t-BuNC)4 with CuBr(t-BuNC)3 in acetone under dinitrogen gives crystals of formula (t-BuNC)4Mo(μ-t-BuS)2CuBr.Two isomers have been isolated in the solid state, differing only in the relative arrangements of tert-butyl substituents on the thiolato bridges.The anti-upright isomer 1 crystallizes from an acetone-toluene mixture with a molecule of diphenylacetylene in a monoclinic cell of dimensions a = 11.702 (2), b = 20.134 (4), and c = 10.455 (4) Angstroem, β = 98.85 (2) deg, Z = 2, and space group P21.Refinement by block-diagonal least-squares methods on F using 3690 unique, diffractometer data converted at R = 0.09.Compound 1 contains a MoS2Cu core, with Mo-Cu = 2.628 (2) Angstroem.The Mo atom has a distorted octahedral coordination geometry, with a large S-Mo-S angle of 105 (1) deg.The Cu atom has almost ideal trigonal-planar geometry.A second isomer, 2, may be crystallized from acetone in the orthorhombic space group Pnma, cell dimensions a = 21.994 (2), b = 16.411 (3), and c = 10.605 (1) Angstroem, with Z = 4.Full-matrix least-squares refinment on F using 2882 averaged data converted at R = 0.08. m symmetry is imposed upon the molecule, which differs from 1 only in the t-Bu substituents on the thiolato bridges adopt a syn-upright conformation.The interconversion of 1 and 2 has been demonstrated by variable-temperature 1H NMR, and values of ΔG* = 7.1 (7) kcal mol-1, ΔH* = 4.9 (2) kcal mol -1, and ΔS* = -6 (2) cal mol-1 deg-1 estimated for the conformational change.
