Metal carbonyl chemistry. Part XVI. Reactions of Prop-2-ynyl compounds with phosphine-substituted carbonylmanganese anions and methyl- and phenyl-pentacarbonylmanganese

Abstract

Prop-2-ynyl chloride forms stable σ-prop-2-ynyl complexes with the anions [Mn(CO)4PPh3]– and [Mn(CO)3(PPh3)2]–. The compound [(CH⋮C·CH2)Mn(CO)4(PPh3)] reacts with the acids RCO2H (R = Me, Et, or ClCH2) to afford stable 1 : 1 adducts of the type [{RCO·O·CH2·(:CH2)}Mn(CO)4(PPh3)], whereas the acids HX (X = Cl, Br, l or CF3·CO2) react to give [XMn(CO)4(PPh3)]. Sulphur dioxide also reacts with [{CH⋮C·CH2}Mn(CO)4(PPh3)] to give the adduct O:[graphic omitted]CH. A number of stable (vinyl ketone)manganese carbonyl complexes, in which the keto-group is co-ordinated to the manganese atom, have been isolated from the reaction of methyl- and phenyl-pentacarbonylmanganese with prop-2-ynyl compounds.