Electron transfer versus nucleophilic pathways in the ion-pair annihilation of organoborate anions by carbonylmanganese(I) cations

摘要: Abstract Substituted carbonylmanganese cations [Mn(CO) 5 L] + , where L=py, PPh 3 and 2 Me, readily react with various organoborate anions (tetramethylborate, methyltriphenylborate tetraphenylborate) in THF solution to afford a mixture of dimanganese carbonyls, hydridomanganese carbonyls alkylmanganese carbonyls. The formation the carbonyl dimers as well suggests involvement 19-electron radicals that stem from an initial electron transfer. On other hand, acetonitrile-substituted analogue (CH CN)] reacts same borate alkylated RMn(CO) R=CH C 6 H sole product. As such, this alkylative annihilation is best formulated direct attack on carbon by nucleophile. two different pathways can be understood terms balance between electrophilicity ligand affinity cation.