Substitution reactions in dinuclear molybdenum(III) thiolato-complexes induced by isocyanato ligands
Résumé
The reactions of [Cp′2Mo2(CO)4(μ-SR) 2](BF4)2 with azido compounds proceeds via a mechanism analogous to the Curtius rearrangement to afford isocyanate species [Cp′2Mo2(NCO)(CO)3(μ-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′2Mo2(NCO)(CO)2(L)(μ-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).