Micro-chlorido, micro-hydroxo-bridged dicarbonyl ruthenacycles: synthesis, structure and catalytic properties in hydrogen atom transfer.

Micro-chlorido, micro-hydroxo-bridged ruthenacycles containing the Ru(CO)2 motif were synthesized by reaction of micro-dichlorido-bridged congener complexes with water in the presence of disodium carbonate. The substitution of one chlorido ligand for one hydroxo occurs with high stereoselectivity affording essentially hydroxo-bridged ruthenacycles, whereby the OH ligand occupies axial positions with respect to the mean plane defined by the chelating ligand. According to computational DFT investigations this stereoselectivity stems from a marked transphobia of the hydroxo ligand towards the carbanion of the ruthenacycle. The catalytic properties of the title compounds in hydrogen atom transfer process and particularly in the partial hydrogenation of alkynes have been investigated.