Synthesis of Acetimino Complexes of Pt(II) and Pt(IV) and the First Heteronuclear μ-Acetimido Complexes

The reactions of [Ag(NHCMe2)2]ClO4 with cis-[PtCl2L2] in a 1:1 molar ratio give cis-[PtCl(NHCMe2)(PPh3)2]ClO4
(1cis) or cis-[PtCl(NHCMe2)2(dmso)]ClO4 (2), and in 2:1 molar ratio, they produce [Pt(NHCMe2)2L2](ClO4)2 [L
= PPh3 (3), L2 = tbbpy = 4,4‘-di-tert-butyl-2,2‘-dipyridyl (4)]. Complex 2 reacts with PPh3 (1:2) to give trans-[PtCl(NHCMe2)(PPh3)2]ClO4 (1trans). The two-step reaction of cis-[PtCl2(dmso)2], [Au(NHCMe2)(PPh3)]ClO4,
and PPh3 (1:1:1) gives [SP-4-3]-[PtCl(NHCMe2)(dmso)(PPh3)]ClO4 (5). The reactions of complexes 2 and 4 with
PhICl2 give the Pt(IV) derivatives [OC-6-13]-[PtCl3(NHCMe2)2(dmso)]ClO4 (6) and [OC-6-13]-[PtCl2(NHCMe2)2(dtbbpy)](ClO4)2 (7), respectively. Complexes 1cis and 1trans react with NaH and [AuCl(PPh3)] (1:10:1.2) to give
cis- and trans-[PtCl{μ-N(AuPPh3)CMe2}(PPh3)2]ClO4 (8cis and 8trans), respectively. The crystal structures of
4·0.5Et2O·0.5Me2CO and 6 have been determined; both exhibit pseudosymmetry.