Synthesis, spectroscopic characterization and structural studies of dimethylsulfoxide and dimethylformamide adducts of bis(mu-sulfido)bis[{O,O-dialkyldithiophosphato}oxomolybdenum(V)] complexes. Crystal structures of Mo2O2(Phi-S-2)[S2P(OEt)(2)](2)cen

摘要

Dimethlsulfoxide and dimethylformamide adducts of bis(mu-sulfido)bis[{O,O-dialkyldithiophosphato} oxomolybdenum(V)] of the type Mo2O2(Phi-S-2)[S2P(OR)(2)](2) . L (R=Me, Et and i-Pr; L=Me2SO and Me2NCHO) were prepared by the dropwise addition of a benzene solution of dimethylsulfoxide or dimethylformamide in excess to a 1:2 benzene-n-hexane solution of bis(mu-sulfido)bis[{O,O-dialkyldithiophosphato}oxomolybdenum(V)]. The compounds, Mo2O2(Phi-S-2)[S2P(OR)(2)](2) . L, were characterized by elemental analysis, IR. and H-1 and P-31 NMR spectroscopy. The crystal structures of Mo2O2(Phi-S-2)[S2P(OEt)(2)](2) . Me2SO, Mo2O2(Phi-S-2)[S2P{O(i-Pr)}(2)](2) . Me2SO and Mo2O2(Phi-S-2)[S2P{O(i-Pr)}(2)](2) . NC5H5 were determined. Mo2O2(Phi-S-2)[S2P(OEt)(2)](2) Me2SO crystallizes in the space group P2(1), with cell parameters a=15.319(3) Angstrom, b=8.750(2) Angstrom, c=20.322(4) Angstrom, beta = 108.55(3)degrees, V=2582.5(9) Angstrom(-3), Z=4, R=0.0277 and R-w=0.0329. Mo2O2(Phi-S-2)[S2P{O(i-Pr)}(2)](2) . Me2SO crystallizes in the space group C2/c, with cell parameters a=29.848(6) Angstrom, b=8.566(2) Angstrom, c=12.328(3)Angstrom, beta=110.03(3)degrees, V=2961.2(10)Angstrom(-3), Z=4, R=0.0272 and R-w=0.0299. Mo2O2(Phi-S-2)[S2P{O(i-Pr)}(2)](2) . NC5H5 crystallizes in the space group P2(1), with cell parameters a=9.210(2) Angstrom, b=28.859(6) Angstrom, c=12.421(3) Angstrom, beta=109.01(3)degrees, V=3121.5(11)Angstrom(-3), Z=4, R=0.0643 and R-w=0.1022. If the Mo-Mo interaction is ignored, the immediate environment about one of the Mo atoms in all three compounds is essentially a distorted octahedral with a very long Mo-O or Mo-N bond, while it is square-pyramidal about the other Mo atom. The terminal oxygen atoms are in the syn conformation. The dithiophosphate groups are bidentate in all complexes. (C) 2003 Elsevier Science B.V. All rights reserved. [References: 40]