Structures and reactivities of cyclopentadienylmolybdenum complexes with oxo and sulfido ligands

Journal Article · Wed May 18 04:00:00 EDT 1988 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00283a016· OSTI ID:7246150

Tanner, L D; Haltiwanger, R C; DuBois, M R ^[1]

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1. Univ. of Colorado, Boulder (USA)

Solutions of (Cp{prime}Mo({mu}-S)({mu}-SH)){sub 2} (Cp{prime} = C{sub 5}H{sub 5}, C{sub 5}H{sub 4}CH{sub 3}) have been oxidized by air to produce syn- and anti(Cp{prime}MoO({mu}-S)){sub 2}. Chromatographic procedures for the isolation of each isomer are reported. The methylcyclopentadienyl derivatives have been characterized by x-ray diffraction studies. The syn isomer crystallizes in space group C2/c with a = 8.214 (2) {angstrom}, b = 11.957 (3) {angstrom}, c = 14.610 (2) {angstrom}, and {beta} = 106.51 (2){degree}. The Mo{sub 2}S{sub 2} unit is bent, and the distance between bridging sulfido atoms is 3.577 {angstrom}, anti-(MeCpMoO({mu}-S)){sub 2} crystallizes in space group P{bar 1} with a = 6.939 (1) {angstrom}, b = 7.197 (1) {angstrom}, c = 7.756 (1) {angstrom}, {alpha} = 103.73 (1){degree}, {beta} = 90.16(1){degree}, and {gamma} = 107.92(1){degree}. Each isomer reacts with ((CH{sub 3}){sub 3}Si){sub 2}S in a reaction that exchanges sulfido for terminal oxo ligands and forms (MeCpMo){sub 2}S{sub 4} derivatives. Intermediate products syn- and anti-(MeCpMo){sub 2}(O)(S)({mu}-S){sub 2} have also been isolated and characterized by spectroscopic methods. syn-(MeCpMo){sub 2}(O)(S)({mu}-S){sub 2} undergoes a disproportionation upon heating to form (MeCpMo){sub 2}O{sub 2}S{sub 2} and (MeCpMo){sub 2}S{sub 4}. Intermolecular oxo/sulfido transfer is also involved in the reaction of syn-(MeCpMo){sub 2}(O)(S)({mu}-S){sub 2} with alkynes, which results in products of the formulations MeCpMo(O)({mu}-S){sub 2}Mo(SCR=C(R)S)-(MeCp) and MeCpMo(O)({mu}-S){sub 2}Mo(OCR=C(R)S)(MeCp). 15 refs., 3 figs., 5 tabs.

• OSTI ID: 7246150
• Journal Information: Inorganic Chemistry; (USA), Journal Name: Inorganic Chemistry; (USA) Vol. 26:10; ISSN 0020-1669; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKENES
COMPLEXES
CRYSTAL STRUCTURE
CYCLOALKENES
CYCLOPENTADIENE
DATA
DIENES
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
ISOMERS
MOLECULAR STRUCTURE
MOLYBDENUM COMPLEXES
NUMERICAL DATA
ORGANIC COMPOUNDS
OXYGEN COMPOUNDS
POLYENES
SULFUR COMPOUNDS
TRANSITION ELEMENT COMPLEXES