Reactions of carbonylmetallate anions with 1-haloalkynesстатья
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Аннотация:The main regularities of the reactions of 1-haloalkynes RC=CX with carbonylmetallate anions [(eta(5)-C5R'(5))(CO)(3)M](-) (R' = H (1-3), M = Cr (1), M = Mo (2), or M = W (3); R' = Me (4-6), M = Cr (4), M = Mo (5), or M = W (6)) were revealed. It was established that the first stage of the reactions of anions 1-6 with bromo- or iodoalkynes RC-CX (X=Br or I) involved the transfer of the halogen atom from the sp-hybridized carbon atom to the transition metal atom to form carbonyl halides (eta(5)-C5R'(5))(CO)(3)MX. To the contrary, the reactions of anions 1-6 with chloroalkynes RC=CCl proceeded selectively as a nucleophilic substitution at the unsaturated carbon atom, the reaction rate being governed by the nucleophilicity of the carbonylmetallate anions and the electron-withdrawing ability of the R group. These reaction paths are consistent with the structures of the lowest unoccupied molecular orbitals (LUMO) in the PhC=CX molecules (X = Cl, Br, or I) calculated by the MNDO/PM3 method. In the case of the reactions of 1-chloroheptyne-1 ClC=CC5H11n, anions 1-3 appeared to be insufficiently nucleophilic, but these reactions can be performed as cross-coupling of the carbonylmetallate anions with chloroalkynes catalyzed by palladium complexes.