화학공학소재연구정보센터
Inorganic Chemistry, Vol.53, No.9, 4585-4597, 2014
Silylamide Complexes of Chromium(II), Manganese(II), and Cobalt(II) Bearing the Ligands N(SiHMe2)(2) and N(SiPhMe2)(2)
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)(mu-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 beta-agostic and M---pi(arene) interactions. Magnetic moments were determined by Evans' method.