SUBSTITUTION REACTIONS IN DINUCLEAR MOLYBDENUM(III) THIOLATO-COMPLEXES INDUCED BY ISOCYANATO LIGANDS

摘要

The reactions of [Cp'Mo-2(2)(CO)(4)(mu-SR)(2)](BF4)(2) with azido compounds proceeds via a mechanism analogous to the Curtius rearrangement to afford isocyanate species [Cp'Mo-2(2)(NCO)(CO)(3)(mu-SR)(2)](BF4) (Cp' = C5H5, R = Me 1, Ph 2; Cp' = C5Me5, R = Me 3). Thermal substitution of CH3CN or R'NC (R' = t-Bu, xylyl, benzyl) for CO in 1-3 results in the formation of monosubstituted derivatives [Cp'Mo-2(2)(NCO)(CO)(2)(L)(mu-SR)(2)](BF4) (L = CH3CN: Cp' = C5H5, R = Me 4, Ph 5; Cp' = C5Me5, R = Me 6; L = R'NC: Cp' = C5Me5, R = Me, R' = t-Bu 7, xylyl 8, benzyl 9). [References: 26]