CATIONIC CARBONYL COMPLEXES OF MANGANESE(I) WITH DIPHOSPHINES

Article abstract of DOI:10.1016/S0022-328X(00)82439-0

The bromo-carbonyls fac-BrMn(CO)3(diphos)(diphos=Ph2P(CH2)nPPh2 for n=1(dpm), 2(dpe), 3(dpp) and 4(dbp)) react with AgClO4 in dichloromethane solution to give the neutral fac-O3ClOMn(CO)3(diphos).The reaction of the latter complexes at room temperature with a variety of ligands L=phosphines (PR3), phosphites P(OR)3), pyridine (Py), acetonitrile (MeCN), tetrahydrothiophene (THT) or acetone (Me2CO) leads to the cationic species fac-ClO4 (or to the ClO4, when L=CO).When L is a phosphorus ligand, the cationic fac-tricarbonyls isomerize upon heating to the mer isomers, which could only be isolated by this method for diphos=dpm, the reaction being accompanied by decomposition in the other cases.UV irradiation of the mer-ClO4 in the presence of a large excess of L gives the corresponding trans-ClO4.