SYNTHESIS AND CHEMISTRY OF THE METALLOLIGAND [CPRU(ETA(2)-DMPM)(ETA(1)-DMPM)]CL - X-RAY CRYSTAL-STRUCTURES OF [CPRU(ETA(2)-DMPM)(PPH(3))]CLAND [CPRU(MU-DMPM)(2)PT(PPH(3))]PF6-CENTER-DOT-CH2CL2

CpRuCl(PPh(3))(2) reacts sequentially with bis(dimethylphosphino)metha ne (dmpm) to yield [CpRu(eta(2)-dmpm)(PPh(3))]Cl (1) and then [CpRu(et a(2)-dmpm)(eta(1)-dmpm)]Cl (2a) from which hexafluorophosphate (2b) an d trifluoromethanesulfonate (2c) salts can be obtained by metathesis. Attempts to synthesize CpRu(X)(eta(1)-dmpm)(2) were largely unsuccessf ul and gave predominantly CpRu(X)(eta(2)-dmpm) (X = CN (3), C=CPh (4)) . In most instances, opening of the chelate ring in 2a did not occur o n reaction with coordinatively unsaturated metal complexes and bi- and trimetallic products such as [CpRu(eta(2)-dmpm)(mu-dmpm)RuCpCl(PPh(3) )]Cl (5), [{CpRu(eta(2)-dmpm)(mu-dmpm)}(2)ML(n)]Cl-2 (ML(n) = PdCl2 (7 ), PtCl2 (8)) and [CpRu(eta(2)-dmpm)(mu-dmpm)RhCl(CO)(PPh(3))] (CF3SO3 ) (9a) resulted. With Pt(C2H4)(PPh(3))(2), however, 2b afforded [CpRu( mu-dmpm)(2)Pt(PPh(3))] PF6 (6). The structures of 1 and 6 were determi ned by X-ray crystallography. Copyright (C) 1996 Elsevier Science Ltd