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

Autor:	Neringa Tamosiunaite, Kuldip Singh, David L. Davies
Rok vydání:	2020
Předmět:	Inorganic Chemistry Steric effects Chemistry Polar effect Electronic effect Substrate (chemistry) Selectivity Medicinal chemistry
Zdroj:	Dalton Transactions. 49:2680-2686
ISSN:	1477-9234 1477-9226
Popis:	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.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::a4cf610944c45cdcd8371bdce6756fb5 https://doi.org/10.1039/c9dt04581c Zobrazit plný text záznamu