Attempts to prepare mixed isothiocyanato-bis(imido) MoVI complexes led to the discovery of post-metathesis rearrangements toward three distinct products (1-3), which feature the NCS-derived chelators [N(NMe2)CS]2- (L1 in dinuclear 1 and 2) and [N(SiMe3)(NMe2)CS]- (L2 in mononuclear 3). Notably, the preparation of bidentate ligand L1 and its coordination chemistry are unprecedented. Together with computational studies, it is proposed that the putative "mono-substituted" intermediate [Mo(NtBu)2(NMe2)(NCS)] serves as the common starting point for the observed molecular transformations. Construction of the [Mo(NtBu)2(NCS)2] core was ultimately possible in the presence of additional stabilizing donors (THF or PMe3), which yielded the complexes [Mo(NtBu)2(NCS)2(THF)2] (4) and [Mo(NtBu)2(NCS)2(PMe3)2] (5).