
Journal of Organometallic Chemistry p. 169 - 178 (1997)
Update date:2022-08-03
Topics:
Becke, Frank
Rueffer, Tobias
Boese, Roland
Blaeser, Dieter
Steinborn, Dirk
Thiomethyl nickel complexes [Ni(CH2SR)2(PBu3)2] (R = Me (1a), tBu (1b), Ph (1c)) and the homoleptic derivatives [{Li(Et2O)}2Ni(CH2StBu)4] (2), [Li2Ni(CH2SMe)4] · x thf (3a) and [Li2Ni(CH2SPh)4] · x Et2O (3b) were synthesized by the reaction of nickel halide phosphine complexes with the appropriate thiomethyl lithium compounds LiCH2SR in a molar ratio of 1/2 and 1/4, respectively. The molecular structures (X-ray) of the diamagnetic heteroleptic derivatives 1 exhibit Ci symmetry with square-planar NiC2P2 units. The ligands are arranged in trans-position. The complexes 1 were characterized by microanalysis and by NMR spectroscopy. The terf-butylthiomethyl complex 2 is stable at room temperature (Tdec. ~ 60-66°C) whereas the methyl- and phenylthiomethyl complexes 3a and 3b are decomposed already at - 10 to - 20°C. The molecular structure (X-ray) of complex 2 shows a slightly distorted planar arrangement of the four methylene carbon atoms and nickel (d(Ni-C) = 1.944(3)-2.004(3) A). The lithium atoms are distorted tetrahedrally coordinated by two sulfur atoms, one oxygen atom (Et2O) and one methylene carbon atom. The short Li-S distances (2.461(6)-2.535(5) A) indicate strong lithium-sulfur interactions.
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