The reaction of rhenium carbonyl with dimethylphenylphosphine and dimethylphenylarsine

Abstract

Dirhenium decacarbonyl reacts with dimethylphenylphosphine and arsine to give compounds [Re(CO) 4(XMe 2Ph)] 2 Re(CO) 3(XMe 2Ph) 2 and Re 2(CO) 7(XMe 2Ph) 3 (X = P or As). Addition of chlorinated solvents to the crude reaction product results in the isolation of additional compounds such as fac-Re(CO) 3(AsMe 2Ph) 2Cl, trans-Re(CO) 3(PMe 2Ph) 2Cl, fac-Re(CO) 3(PMe 2Ph) 2Cl and Re(CO) 2(PMe 2Ph) 3Cl. Reactions of [Re(CO) 4(PMe 2Ph)] 2 and [Re(CO) 4(AsMe 2Ph)] with hydrochloric acid gas and halogens results in the formation of halogeno compounds cis-Re(CO) 4(PMe 2Ph)Cl, cis- and trans-Re(CO) 4(PMe 2Ph)Br, cis- and trans-Re(CO) 4(PMe 2Ph)I, cis-Re(CO) 4(AsMe 2Ph)Cl and cis-Re(CO) 4(AsMe 2Ph)Br. The compound Re 2(CO) 7(PMe 2Ph) 3 reacts with dry HCl gas, molar quantities of bromine and iodine to give the compounds, trans-Re(CO) 3(PMe 2Ph) 2Cl, trans-Re(CO) 3(PMe 2Ph) 2Br, trans-Re(CO) 3(PMe 2Ph) 2I, cis-Re(CO) 4(PMe 2Ph)Cl, cis-Re(CO) 4(PMe 2Ph)Br and trans-Re(CO) 4(PMe 2Ph)I. When Re 2(CO) 7(PMe 2Ph) 3 was reacted with an excess of bromine at 0° the compounds Re(CO)(PMe 2Ph) 2Br 3 and Re(PMe 2Ph) 2Br 4 were isolated. The IR and proton NMR spectra of these new compounds are discussed. The mass spectra of a number of these compounds have been recorded and are also discussed.