TERT-BUTYLIMIDO COMPLEXES OF CHROMIUM - X-RAY CRYSTAL-STRUCTURES OF CR(NBU-TERT)2(PME2PH)CL2 AND [CR(NBU-TERT)2(C5H4N)2(ETA-1-O3SCF3)]O3SCF3

The compound Cr(NBut)2Cl2 has been synthesized and converted to Cr(NBut)2(NHBut)Cl, Cr(NBut)2(NHBut)2 and Li2 Cr(NBut)4, the latter completing the series of Group 6 compounds, Li2 M(NBut)4, M = Cr, Mo, W. The five-coordinate adducts, Cr(NBut)2Cl 2L, L = PMe3, PMe2Ph and ButNC, have been characterized as well as [Cr(NBut)2Cl2]2(μ-Ph2PCH2CH2PPh2) and the six-coordinate Cr(NBut)2Cl2(2,2′-bipyridyl). Chloride substitution reactions of Cr(NBut)2Cl2 lead to the compounds, Cr(NBut)2(η1-O 2CMe)2, [Cr(NBut)2(PMe3)2](O3SCF3)2·0.5MeCN, [Cr(NBut) 2py2(η1-O3SCF3)]SO3CF3 and [Cr(NBut)2(bpy)2](PF6) 2. The isocyanide, [Cr(NBut)2Cl2(ButNC)], with MeLi gives the η2-iminoacyl Cr(NBut)2[η2-(ButNCMe)]Cl. Interaction of Cr(NBut)2Cl2 with alkylating agents at low temperatures gives the chromium(V) dimer [Cl(ButN)Cr(μ-NBut)] 2 in a one-electron per chromium reduction and the same product is obtained by reduction of the dihalide with (η5-C5H5)2Co. X-ray structures of compounds listed in the title have been determined. © 1990.