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Carbonylmetallates—A Special Family of Nucleophiles in Aromatic and Vinylic Substitution Reactions
Author(s) -
Sazonov Petr K.,
Beletskaya Irina P.
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201504423
Subject(s) - nucleophile , chemistry , carbanion , electrophile , reactivity (psychology) , aryl , substitution reaction , medicinal chemistry , nucleophilic aromatic substitution , heteroatom , nucleophilic substitution , photochemistry , organic chemistry , catalysis , alkyl , medicine , alternative medicine , pathology
Carbonylmetallates, [M(CO) n L] − , anionic transition‐metal carbonyl complexes, represent a large family of metal‐centered nucleophiles, and studying carbonylmetallates allows us to understand the differences in the behavior of the metal‐centered complexes versus heteroatom‐based nucleophiles. The mechanisms of carbonylmetallate reactions with aryl‐ and alkenyl halides have been examined by employing radical and, especially, carbanion trapping techniques. Carbonylmetallates show a marked preference for halogenophilic attack, and nucleophilic substitution with carbonylmetallates is often not a direct process, but proceeds through the initial attack at halogen with subsequent coupling of carbanion and HalM(CO) n L intermediates. Factors governing the competition between the halogenophilic and more common “carbophilic” reaction pathways, as well as the means of predicting the actual course of reaction are discussed. The review also considers other aspects of carbonylmetallate reactivity, including ion‐pairing effects, radical‐mediated nucleophilic substitution pathways, and the carbonylmetallate nucleophilicity scale in the reactions with π‐electrophiles.