Steric and electronic effects on acetate-assisted cyclometallation of 2-phenylpyridines at [MCl2Cp*]2 (M = Ir, Rh)

被引：5

作者：

Davies, David L. ^{[1
]}

Singh, Kuldip ^{[1
]}

Tamosiunaite, Neringa ^{[1
]}

机构：

[1] Univ Leicester, Dept Chem, Leicester LE1 7RH, Leics, England

来源：

DALTON TRANSACTIONS | 2020年 / 49卷 / 08期

基金：

英国工程与自然科学研究理事会;

关键词：

H BOND ACTIVATION; METALATION-DEPROTONATION MECHANISM; FLUORINE SUBSTITUENTS; DIRECT ARYLATION; SELECTIVITY; REGIOSELECTIVITY; COMPLEXES; KINETICS; SENSITIVITY;

D O I：

10.1039/c9dt04581c

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The reactions of substituted 2-phenylpyridines at [MCl2Cp*](2) dimers (M = Ir, Rh) in the presence of NaOAc form cyclometallated complexes Cp*M(Phpyr)Cl. H/D exchange experiments and substrate competition experiments show that kinetic selectivity favours electron donating substituents whilst substrates with electron withdrawing substituents are favoured thermodynamically. Experiments with Ir are mostly irreversible under the conditions used whilst those for Rh are more easily reversible. For meta-substituted phenylpyridines steric effects are important, larger substituents leading to formation of the para-substituted cyclometallated product.

引用

页码：2680 / 2686

页数：7

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