Insights into the decomposition pathway of a lutetium alkylamido complex via intramolecular C-H bond activation

被引：8

作者：

Knott, Jackson P. ^{[1
]}

Hanninen, Mikko M. ^{[1
,2
]}

Rautiainen, J. Mikko ^{[2
]}

Tuononen, Heikki M. ^{[2
]}

Hayes, Paul G. ^{[1
]}

机构：

[1] Univ Lethbridge, Dept Chem & Biochem, 4401 Univ Dr, Lethbridge, AB T1K 3M4, Canada

[2] Univ Jyvaskyla, Dept Chem, POB 35, FI-40014 Jyvaskyla, Finland

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2017年 / 845卷

基金：

加拿大创新基金会; 加拿大自然科学与工程研究理事会; 芬兰科学院;

关键词：

TERMINAL IMIDO COMPLEX; EARTH-METAL COMPLEXES; BASIS-SETS; ANILIDO-PHOSPHINIMINE; SCANDIUM; REACTIVITY; EXISTENCE; BEHAVIOR; VALENCE; METHYL;

D O I：

10.1016/j.jorganchem.2017.04.008

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Synthesis, characterization and reaction chemistry of lutetium alkylamido LLu(CH2SiMe3)(NHCPh3) (2), L - 2,5-[Ph2P-N(4-(PrC6H4)-Pr-i)](2)N(C4H2)(-), is reported. Complex 2 undergoes cyclometalation of the NHCPh3 ligand at elevated temperatures to produce the orthometalated complex LLu(k(2-N,C)-(NHCPh2(C6H4))) (3) which converts to 0.5 equivalents of bis(amido) LLu(NHCPh3)(2) (4) upon heating at 80 degrees C for 24 h. Reaction of complex 2 with 4-dimethylaminopyridine (DMAP) does not promote alkane elimination nor imido formation. A kinetic analysis of the thermal decomposition of complex 2, supported by deuterium labelling studies and computational analysis (PBE0/def2-TZVP/SDD(Lu)), indicate direct C-sp2-H activation, rather than C-H addition across a transient LLu=NCPh3 species, occurs. (C) 2017 Elsevier B.V. All rights reserved.

引用

页码：135 / 143

页数：9

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