由钽酰胺硅基配合物与氧气反应合成及表征甲硅烷氧基、氨氧基和氧代配合物。

Synthesis and characterization of siloxy, aminoxy, and oxo complexes from the reaction of a tantalum amide silyl complex with oxygen.

作者信息

Qiu He, Chen Shu-Jian, Wang Chang-Sheng, Wu Yun-Dong, Guzei Ilia A, Chen Xue-Tai, Xue Zi-Ling

机构信息

Department of Chemistry, The University of Tennessee, Knoxville, Tennessee 37996, USA.

出版信息

Inorg Chem. 2009 Apr 6;48(7):3073-9. doi: 10.1021/ic802380u.

DOI:10.1021/ic802380u

PMID:19245230

Abstract

(Me(2)N)(4)Ta-SiBu(t)Ph(2) (1) reacts with O(2) to give (Me(2)N)(4)Ta(OSiBu(t)Ph(2)) (2), (Me(2)N)(3)Ta(ONMe(2))(OSiBu(t)Ph(2)) (3), and the unusual mu-oxo amino (Me(2)N)(2)(Ph(2)Bu(t)SiO)(2)(mu,eta(2)-Me(2)NCH(2)NMe)(2)Ta(2)(mu-O)(2) (4) containing two bridging chelating (aminomethyl)amides -N(Me)CH(2)NMe(2). The dimer 4 was characterized by X-ray crystallography. 2 also reacts with O(2) to give both 3 and 4. Reaction pathways in the formation of these complexes are discussed. In reactions of O(2) with d(0) 1 and 2, oxidation of the ligands is the prevailing pathway.

摘要

（二甲基氨基）₄钽-叔丁基二苯基硅基（1）与氧气反应生成（二甲基氨基）₄钽-氧代叔丁基二苯基硅基（2）、（二甲基氨基）₃钽-氧代二甲基氨基-氧代叔丁基二苯基硅基（3）以及不寻常的μ-氧代氨基（二甲基氨基）₂（叔丁基二苯基硅氧基）₂（μ，η²-二甲基氨基甲基二甲基氨基）₂钽₂（μ-O）₂（4），其含有两个桥连螯合（氨基甲基）酰胺-N（Me）CH₂NMe₂。二聚体4通过X射线晶体学进行了表征。2也与氧气反应生成3和4。讨论了这些配合物形成过程中的反应途径。在氧气与d⁰的1和2的反应中，配体的氧化是主要途径。