Chiral Organometallic Triangles with Rh−Rh Bonds. 1. Compounds Prepared from Racemic <i>cis</i>-Rh<sub>2</sub>(C<sub>6</sub>H<sub>4</sub>PPh<sub>2</sub>)<sub>2</sub>(OAc)<sub>2</sub>
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Reaction of racemic cis-Rh2(C6H4PPh2)2(OAc)2(HOAc)2 with excess Me3OBF4 in CH3CN results in the formation of racemic cis-[Rh2(C6H4PPh2)2(CH3CN)6](BF4)2·0.5H2O (1·0.5H2O), 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 tetraethylammonium salts of the linear dicarboxylates, oxalate, terephthalate, and 4,4‘-biphenyl-dicarboxylate, in organic solvents, produced racemic crystals of the triangular compounds [Rh2(C6H4PPh2)2]3(C2O4)3(py)6·6MeOH·H2O (2·6MeOH·H2O), [Rh2(C6H4PPh2)2]3(O2CC6H4CO2)3(DMF)6·6.5DMF·0.5H2O (3·6.5DMF·0.5H2O), and [Rh2(C6H4PPh2)2]3(O2CC6H4C6H4CO2)3(py)6·4.5CH3OH·0.75H2O (4·4.5CH3OH·0.75H2O), 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 31P NMR spectroscopy.
