Synthesis and characterization of new homo-heterobinuclear platinum(II) complexes with dimethylphosphonate as bridging ligands. Crystal structure of [(eta(2)dppm)Pt{mu-P(O)(OMe)(2)}(2)(mu-I)PtMe(3)]

Abstract

The preparation of the new neutral complex [(eta(2)-dppm)Pt{P(O)(OMe)(2)}(2)] (1) (dppm = 1,1-bis(diphenylphosphino) methane) and its behaviour as a chelate (O,O)-donor ligand is described. This ligand reacts with [Me(3)PtI](4) to give the homobimetallic complex [(eta(2)dppm)Pt{mu-P(O)(OMe)(2)}(2)(mu-I)PtMe(3)] (2), which in turn reacts with AgPF6 in the presence of PPh(3) to yield the new cationic complex [(eta(2)dppm)Pt{mu-P(O)(OMe)(2)}(2){PtMe(3)(PPh(3))}]PF6 (3). In contrast, the treatment of binuclear complexes [{Pd(mu-Cl)(2-MeC(3)H(4))}(2)] and [{Rh(mu-Cl)(cod)}(2)] with silver perchlorate in the presence of the bidentate ligand 1 yields the heterobinuclear compounds [(eta(2)dppm)Pt{mu-P(O)(OMe)(2)}Pd-2(eta(3)MeC(3)H(4))]ClO4 (4) and [(eta(2)dppm)Pt{mu-P(O)(OMe)(2)}Rh-2(cod)]ClO4 (5). Complex 5 reacts with an atmosphere of CO at room temperature yielding the cis-dicarbonyl complex [(eta(2)dppm)Pt{mu-P(O)(OMe)(2)}Rh-2(CO)(2)]ClO4 (6). The structure of complex [(eta(2)dppm)Pt{mu-P(O)(OMe)(2)}(2)(mu-I)PtMe(3)] has been determined by single crystal X-ray diffraction methods.