SYNTHESIS, CHARACTERIZATION, AND REACTIVITY OF AN OXORUTHENIUM(IV) COMPLEX CONTAINING A BIS(OXAZOLINE) LIGAND - CRYSTAL-STRUCTURE OF [RU((S)-BPOP)(CL)(TRPY)](BF4)
Lf. Szczepura et al., SYNTHESIS, CHARACTERIZATION, AND REACTIVITY OF AN OXORUTHENIUM(IV) COMPLEX CONTAINING A BIS(OXAZOLINE) LIGAND - CRYSTAL-STRUCTURE OF [RU((S)-BPOP)(CL)(TRPY)](BF4), Inorganic chemistry, 34(16), 1995, pp. 4198-4205
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.