Synthesis, characterization, and reactivity of an oxoruthenium (IV) complex containing a Bis(oxazoline) ligand: Crystal structure of [Ru((S)-bpop)(Cl)(trpy)](BF{sub 4})

Journal Article · Wed Aug 02 04:00:00 EDT 1995 · Inorganic Chemistry

DOI:https://doi.org/10.1021/ic00120a027· OSTI ID:160103

Szczepura, L F; Maricich, S M; See, R F ^[1]

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1. State Univ. of New York, Buffalo, NY (United States); and others

The synthesis and characterization of two [Ru(L)(O)(trpy)](ClO{sub 4}){sub 2} complexes (where trpy = 2,2{prime}:6{prime},2{double_prime}-terpyridine and L=(S)- or (R)-bpop = 2,2-bis[2-[4(S)- or 4(R)-phenyl-1,3-oxazolinyl]]propane) are described. These complexes are among the first high oxidation state oxoruthenium complexes which contain an optically active ligand fixed in a position cis to the oxo moiety. The preparations of the precursor materials, [Ru(L)(Cl)(trpy)]- (BF{sub 4}) and [Ru(H{sub 2}O)(L)(trpy)](BF{sub 4})2, are also described. A single-crystal X-ray diffraction analysis of [Ru((S)-bpop)(Cl)(trpy)](BF{sub 4}) was undertaken. The crystals belong to the monoclinic system, space group P2{sub 1}, with a = 12.1507(16) {Angstrom}, b=12.3633(10) {Angstrom}, c=12.4606 (14) {Angstrom},{beta}=113.332(9){degrees}, V=171839(3) {Angstrom}{sup 3}, and Z=2. The structure was solved and refined to R=2.28% and R{sub w}=2.98% for all 6085 independent reflections. (R=1.99% for those 5680 reflections with F{sub o}>6{sigma}(F{sub o}).) This is the first report of a (bis(oxazoline)) ruthenium single-crystal X-ray structural analysis. To establish the viability of these complexes for ligand effect studies, the pK{sub a} value of the bpop ligand was measured along with the rate constant for the ligand substitution of the aqua ligand of [Ru(H{sub 2}O)((R)-bpop)(trpy)](ClO{sub 4})2 by acetonitrile. The authors` initial substrate oxidation studies of these new (bis-(oxazoline))oxoruthenium(IV) complexes with methyl p-tolyl sulfide or racemic methyl p-tolyl sulfoxide yield results consistent with previous mechanistic studies on sulfide and sulfoxide oxidations with oxo(phosphine)-ruthenium (IV) complexes.

• Sponsoring Organization: USDOE
• OSTI ID: 160103
• Journal Information: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 16 Vol. 34; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CRYSTAL STRUCTURE
MONOCLINIC LATTICES
OXIDATION
RUTHENIUM COMPLEXES
SULFIDES
SULFOXIDES