Reactions of d0 group 4 amides with dioxygen. Preparation of unusual oxo aminoxy complexes and theoretical studies of their formation.
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.
Wang
Ruitao
R
Department of Chemistry, The University of Tennessee, Knoxville, Tennessee 37996-1600, USA.
Zhang
Xin-Hao
XH
Chen
Shu-Jian
SJ
Yu
Xianghua
X
Wang
Chang-Sheng
CS
Beach
David B
DB
Wu
Yun-Dong
YD
Xue
Zi-Ling
ZL