Synthesis and reactivity of novel niobocene complexes containing allyl or 1-azaallyl ligands. X-ray crystal structure of [Li{eta(3)-N(SiMe3)C(Bu-t)CH2}](3)

摘要

The lithium 1-azaallyl complex [LiC{eta(3)-N(SiMe3)C(Bu-t)CH2}](3) (1), has been prepared, and its X-ray crystal structure was determined. The niobocene(III) allyl and 1-azaallyl complexes Cp'Nb-2[eta(3)-CH2C(R)CH2] (Cp' = eta(5)-C5H4SiMe3; R = H (2), Me (3)) and Cp'Nb-2[N(SiMe3)C(Bu-t)CH2] (4) have been synthesized. Oxidation of 2 and 3 by O-2 yields Cp'Nb-2[eta(1)-CH2C(R)CH2](O) (R = H (5), Me (6)). The complexes CpNb(=(NBu)-Bu-t)[eta(1)-CH2C(R)CH2]Cl (Cp = eta(5)-C5H5; R = H (7), Me (8)) have also been prepared. Oxidation of 2-4 by PbCl2 gave Cp'Nb-2[eta(1-)CH(2)C(R)CH2]Cl (R = H (9), Me (10)) and Cp'Nb-2[N(SiMe3)C(Bu-t)CH2]Cl (11). Cp'Nb-2[eta(1)-CH2C(R)CH2](L) (L = CO (12), CN(2,6-Me-2-C6H3) (13)) were prepared by the reaction of Cp'2NbCl(L) with ClMg(CH2CHCH2). [References: 36]