Diverse Post-Metathesis Reactivities of Mixed Amido-Isothiocyanato Molybdenum Complexes.

Attempts to prepare mixed isothiocyanato-bis(imido) Mo complexes led to the discovery of post-metathesis rearrangements toward three distinct products (-), which feature the NCS-derived chelators [N(NMe)CS] ( in dinuclear and ) and [N(SiMe)(NMe)CS] ( in mononuclear ). Notably, the preparation of bidentate ligand and its coordination chemistry are unprecedented. Together with computational studies, it is proposed that the putative "mono-substituted" intermediate [Mo(NBu)(NMe)(NCS)] serves as the common starting point for the observed molecular transformations. Construction of the [Mo(NBu)(NCS)] core was ultimately possible in the presence of additional stabilizing donors (THF or PMe), which yielded the complexes [Mo(NBu)(NCS)(THF)] () and [Mo(NBu)(NCS)(PMe)] ().