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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 19, Number 11
BKCSDE 19(11)
November 20, 1998 

Electrophilic Attack of the Phenyl Isocyanate Carbon at the Bridging Imido Nitogen: Preparation and Structure of Mo2{μ-N(CONPh)Ph}{μ-NPh)(NPh)2(S2CNEt2)2
Gyung Kim, Soon W. Lee
Bis(diethyldithiocarbamato)ioxomolybdenum(VI), cis-MoO2(S2CNEt2)2, 1, reacted with chlorotrimethylsilane (Me33SiCl) to give a seven-coordinate, pentagonal bipyramidal complex MoOC12(S2CN]Et2)2, 3, in which the oxo ligand is trans to the chloride ligand and the two chloride ligands are mutually cis. The monooxo molybdenum complex bis(diethyidithiocarbamato)oxomolybdenum(IV), MoO(S2CNEt2)2, 2, reacted with phenyl isocyanate (PhNCO) to give an Mo dimer MO2{μ-N(CONPh)Ph}(μ-NPh)(NPh)2(S2CNEt2)2, 4, which contains an Mo-Mo bond, two diethyldithiocarbamato ligands, two terminal imido (NPh) ligands, and two bridging hnido (NPh) ligands. One of the two bridging NPh ligands seemed to have been attacked by the electrophilic phenyl isocyanate carbon, which suggests that the bridging imido NPh ligand is more nucleophilic than the terminal one. Crystallographic data for 3: monoclinic space group P21/c, a=8.908(l) Å, b=17.509(3) Å, c=12.683(2) Å, β=110.15(1)°, Z=4, R(wR2)=0.0611(0.1385). Crystallographic data for 4-THF: orthorhombic space group P212121, a=17.932(4) Å, b=22.715(5) Å, c=11.802(3) Å, Z=4, R(wR2)=0.0585(0.1286).
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