title: Carbonylmetallates--A Special Family of Nucleophiles in Aromatic and Vinylic Substitution Reactions.
abstract: 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.
authors.affiliation: Chemistry Department, Moscow State University, Leninskie Gory, 1, 119992, Moscow, Russia.
authors.forename: Petr K
authors.initials: PK
authors.lastname: Sazonov
authors.affiliation: Chemistry Department, Moscow State University, Leninskie Gory, 1, 119992, Moscow, Russia. beletska@org.chem.msu.ru.
authors.forename: Irina P
authors.initials: IP
authors.lastname: Beletskaya
keywords: carbonylmetallates; halogenophilic reactions; nucleophilic aromatic substitution; nucleophilic vinylic substitution; transition metals