Reactions of hexacarbonylrhenium(I) perchlorate with phosphines and other ligands

Abstract

Hexacarbonylrhenium perchlorate, [Re(CO) 6 ]ClO 4 , reacts on heating above 120° with 1,2-bis(diphenylphosphino)ethane and with triphenylphosphine to form respectively [Re(CO) 4 (Ph 2 C 2 H 4 PPh 2 )]ClO 4 and trans-Re(CO) 3 (PPh 3 ) 2 Cl. The stereochemistry of trans-Re(CO) 3 (PPh 3 ) 2 Cl was established by dipole moment and infrared measurements. Other phosphines failed to yield clean products. The reactions of phosphines and other ligands with [Re(CO) 6 ]ClO 4 are discussed, in particular the reaction with triphenylphosphine in which the perchlorate is reduced to chloride and incorporated by rhenium to form trans-Re(CO) 3 (PPh 3 ) 2 Cl.