Achiral [Ru-2(mu-O2CR)(4)(MeOH)(2)](PF6) (R = CH3 or C6H5) reacts with the chiral diphosphines R,R- and S,S-Chiraphos (two chiral centers on ligand between the coordinating P atoms) and R-Prophos (one chiral center on ligand between the coordinating P atoms) leading to a disassembly of the paddlewheel core and the highly diastereoselective production of Lambda-[Ru(eta(2)-O2CC6H5)(eta(2)-R,R-Chiraphos)(2)](PF6) (Lambda-R,R-III), Delta-[Ru(eta(2)center dot O2CC6H5)(eta(2)-S,S-Chiraphos)(2)](PF6) (Delta-S,S-III) (the R = CH3 complexes of Chiraphos were reported in a earlier communication in this journal), and Lambda-[Ru(eta(2)-O2CCH3)(eta(2)-R-Prophos)(2)](PF6) (Lambda-R,R-VI), respectively, in high yield and purity. Reactions of the same starting material with R,R- and S,S-o-tolyl-Dipamp (chiral centers are the coordinating P-atoms) lead to an inversion in the chirality-at-metal producing Lambda-[Ru(eta(2)-O2CC6H5)(eta(2)-S,S-o-tolyl-Dipamp)(2)] (PF6) (Lambda-S,S-IV), Delta-[Ru(eta(2)-O2CC6H5)(eta(2)-R,R-o-tolyl-Dipamp)(2)](PF6) (Delta-R,R-IV), Lambda-[Ru(eta(2)-O2CCH3)(eta(2)-S,S-o-tolyl-Dipamp)(2))(PF6) (Lambda-S,S-V), and Delta-[Ru(eta(2)-O2CCH3)(eta(2)-R,R-o-tolyl-Dipamp)(2)](PF6) (Delta-R,R-V). X-ray crystallography of all but Lambda-S,S-V and Delta-R,R-V and solid-state circular dichroism (CD) show that only the indicated diastereomers are present in the solid-state. Solution CD measurements and P-31 NMR also indicate their predominance in solution.