Abstract

Bis(dimethylsilyl)amide and bis(dimethylphenylsilyl)amide complexes of the divalent transition metals chromium, manganese, and cobalt were synthesized. Dimeric, donor-free {Mn[N(SiHMe2)2]2}2 could be obtained via two different pathways, a salt metathesis route (utilizing MnCl2(thf)1.5 and LiN(SiHMe2)2) and a transsilylamination protocol (utilizing Mn[N(SiMe3)2]2(thf) and HN(SiHMe2)2). Addition of 1,1,3,3-tetramethylethylendiamine (tmeda) to {Mn[N(SiHMe2)2]2}2 yielded the monomeric adduct Mn[N(SiHMe2)2]2(tmeda). The syntheses of Cr[N(SiHMe2)2]2(tmeda), Co[N(SiMe3)2][N(SiHMe2)2](tmeda), and Co[N(SiHMe2)2]2(tmeda) were achieved by transsilylamination from Cr[N(SiMe3)2]2(tmeda) and {Co[N(SiMe3)2]2}2(μ-tmeda), respectively. Bis(dimethylphenylsilyl)amide complexes Mn[N(SiMe2Ph)2]2, Cr[N(SiMe2Ph)2]2, and Co[N(SiMe2Ph)2]2(thf) were obtained via salt metathesis employing MCl2(thf)x (M = Cr, Mn, Co) with equimolar amounts of LiN(SiMe2Ph)2 in n-hexane. Treatment of CrCl2 with LiN(SiMe2Ph)2 in thf gave Cr[N(SiMe2Ph)2]2(thf)2, featuring an almost square planar trans-coordination. All complexes were examined by elemental analyses, DRIFT and UV-vis spectroscopy, as well as X-ray structure analysis, paying particular attention to secondary M---SiH β-agostic and M---π(arene) interactions. Magnetic moments were determined by Evans' method.

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