Chiral organometallic triangles with Rh-Rh bonds.: 1.: Compounds prepared from racemic cis-Rh2(C6H4PPh2)2(OAc)2

Reaction of racemic cis-Rh-2(C6H4PPh2)(2)(OAc)(2)(HOAC)(2) with excess Me3OBF4 in CH3CN results in the formation of racemic cis-[Rh-2(C(6)H(4)Pph(2))(2)(CH3CN)(6)](BF4)(2).0.5H(2)O (1.0.5H(2)O), an ionic dirhodium complex which has two cisoid nonlabile orthometalated phosphine bridging anions and six labile CH3CN ligands in equatorial and axial positions. Reactions of 1 with tetraethylammoniurn salts of the linear clicarboxylates, oxalate, terephthalate, and 4,4'-biphenyl-dicarboxylate, in organic solvents, produced racemic crystals of the triangular compounds [Rh-2(C6H4PPh2)(2)](3)(C2O4)(3)(PY)(6-6)MeOH-H2O (2.6MeOH.H2O), [Rh-2(C6H4PPh2)2]3(O2CC6H4CO2)(3)(DMF)(6).6.5DMF.0.5H(2)O (3(.)6.5DMF.0.51-H2O), and [Rh-2(C6H4PPh2)(2)](3)(O2CC6H4C6H4CO2)(3)(PY)(6)(.)4.45CH(3)OH.0.75H(2)O (4(.)4.5CH(3)OH(.)0.75H(2)O), respectively. All compounds are electrochemically active. The relative chiralities of the dirhodium units in each triangle have been established using a combination of data from X-ray crystallography and P-31 NMR spectroscopy.