SYNTHESIS, CHARACTERIZATION, AND REACTIVITY OF AN OXORUTHENIUM(IV) COMPLEX CONTAINING A BIS(OXAZOLINE) LIGAND - CRYSTAL-STRUCTURE OF [RU((S)-BPOP)(CL)(TRPY)](BF4)

The synthesis and characterization of two [Ru(L)(O)(trpy)](ClO4)(2) co mplexes (where trpy = 2,2':6',2 ''-terpyridine and L = (S)- or (R)-bpo p = 2,2-bis[2-[4(S)- or 4(R)-phenyl-1,3-oxazolinyl]]propane) are descr ibed. These complexes are among the first high oxidation state oxoruth enium complexes which contain an optically active ligand fixed in a po sition cis to the oxo moiety. The preparations of the precursor materi als, [Ru(L)(Cl)(trpy)]-(BF4) and [Ru(H2O)(L)(trpy)](BF4)(2), are also described. A single-crystal X-ray diffraction analysis of [Ru((S)-bpop )(Cl)(trpy)](BF4) was undertaken. The crystals belong to the monoclini c system, space group P2(1), with a = 12.1507(16) Angstrom, b = 12.363 3(10) Angstrom, c 12.4606 (14) Angstrom, beta = 113.332(9)degrees. V = 1718.9(3) Angstrom(3), and Z = 2. The structure was solved and refine d to R = 2.28% and R(w) = 2.98% for all 6085 independent reflections. (R = 1.99% for those 5680 reflections with F-0 > 6 sigma(F-0).) This i s the first report of a (bis(oxazoline))ruthenium single-crystal X-ray structural analysis. To establish the viability of these complexes fo r ligand effect studies, the pK(2) value of the bpop ligand was measur ed along with the rate constant for the ligand substitution of the aqu a ligand of [Ru(H2O)((R)-bpop)(trpy)](ClO4)(2) by acetonitrile. Our in itial substrate oxidation studies of these new (bis(oxazoline))oxoruth enium (IV) complexes with methyl p-tolyl sulfide or racemic methyl p-t olyl sulfoxide yield results consistent with our previous mechanistic studies on sulfide and sulfoxide oxidations with oxo(phosphine)rutheni um (IV) complexes.