title: Reactions of d0 group 4 amides with dioxygen. Preparation of unusual oxo aminoxy complexes and theoretical studies of their formation.
abstract: Reactions of d0 amides M(NMe2)4 (M = Zr, 1; Hf, 2) with O2 have been found to yield unusual trinuclear oxo aminoxide complexes M3(NMe2)6(mu-NMe2)3(mu3-O)(mu3-ONMe2) (M = Zr, 3; Hf, 4) in high yields. Tetramethylhydrazine Me2N-NMe2 was also observed in the reaction mixtures. Crystal structures of 3 and 4 have been determined. Density functional theory calculations have been performed to explore the mechanistic pathways in the reactions of model complexes Zr(NR2)4 (R = H, 5; Me, 1) and [Zr(NR2)4]2 (R = H, 5a; Me, 1a) with triplet O2. Monomeric and dimeric reaction pathways in the formation of the Zr complex 3 are proposed.
authors.affiliation: Department of Chemistry, The University of Tennessee, Knoxville, Tennessee 37996-1600, USA.
authors.forename: Ruitao
authors.initials: R
authors.lastname: Wang
authors.forename: Xin-Hao
authors.initials: XH
authors.lastname: Zhang
authors.forename: Shu-Jian
authors.initials: SJ
authors.lastname: Chen
authors.forename: Xianghua
authors.initials: X
authors.lastname: Yu
authors.forename: Chang-Sheng
authors.initials: CS
authors.lastname: Wang
authors.forename: David B
authors.initials: DB
authors.lastname: Beach
authors.forename: Yun-Dong
authors.initials: YD
authors.lastname: Wu
authors.forename: Zi-Ling
authors.initials: ZL
authors.lastname: Xue