Thermolysis of Ru3(CO)8(µ-dppm)(µ-dpam): Transformation of bis(diphenylphosphino)methane and bis(diphenylarsino)methane

Abstract Heating Ru 3 (CO) 8 (µ-dppm)(µ-dpam) ( 1 ) for 5 h in refluxing toluene resulted in the formation of Ru 3 (µ-H)(CO) 7 (µ 3 -PhPCH 2 PPh 2 (C 6 H 4 )As)(µ 3 -CHAsPh 2 ) ( 2 ), Ru 3 (µ-H)(CO) 7 (µ 3 -PhPCHPPh(C 6 H 4 ))(µ-dpam) ( 3 ), Ru 3 (CO) 7 (µ 3 -PPh)(µ 3 -CHPPh 2 )(µ-dpam) ( 4 ), Ru 3 (µ-CO)(CO) 6 (µ 3 -Ph 2 PCH 2 PPh)(µ 3 -Ph 2 AsCH 2 As(C 6 H 4 )Ph) ( 5 ) and Ru 3 (µ 3 -O)(µ 3 -CO)(CO) 5 (µ-dppm)(µ-dpam) ( 6 ). The reaction involves C–H, P–C and As–C bonds activation, elimination of benzene and unusual metalation of the P(C 6 H 4 )As. All the new clusters have been characterized by a combination of spectroscopic data and single crystal X-ray diffraction analysis.