Reactivity studies of sulfur-bridged molybdenum dimers containing electron-withdrawing dithiolate substituents

Journal Article · Wed Dec 01 04:00:00 EST 1993 · Organometallics; (United States)

DOI:https://doi.org/10.1021/om00036a016· OSTI ID:5115964

Lopez, L L; Gabay, J; Haltiwanger, R C; Green, K; Allshouse, J; Casewit, C; DuBois, M R ^[1]

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1. Univ. of Colorado, Boulder, CO (United States)

New complexes of the formula (Cp[prime]Mo([mu]-S))[sub 2]S[sub 2]CHR, where R = CO[sub 2]Me (3) and CO[sub 2]Na (4) (Cp[prime] = C[sub 5]H[sub 5], CH[sub 3]C[sub 5]H[sub 4]), have been synthesized and characterized spectroscopically. Their reactions have been compared to those of the parent compound, where R = H (1). The synthesis of 3 involved the alkylation of (MeCpMo)[sub 2]([mu]-S[sub 2])([mu]-S)[sub 2] with BrCH[sub 2]CO[sub 2]Me to form [(MeCpMo)[sub 2]-([mu]-S[sub 2])([mu]-SCH[sub 2]CO[sub 2]Me)]Br (2(Br)). Complex 2 crystallized in space group P2[sub 1]/c with a = 10.379(2) [angstrom], b = 20.820(6) [angstrom], c = 9.597(2) [angstrom], [beta] = 102.56[degrees], V = 2024.3(8) [angstrom][sup 3], and Z = 4. An X-ray diffraction study of 2 confirmed that a [mu]-sulfido ligand was the site of alkylation and the [mu]-S[sub 2] ligand remained intact. Complex 2 was deprotonated on an alumina column to form 3. The water-soluble complex 4 was synthesized by the reaction of [Cp[prime]Mo([mu]-S)([mu]-SH)][sub 2] with Br[sub 2]CHCO[sub 2]Na in the presence of base. The reactivities of 3 and 4 are similar to that of 1 in most cases. Unlike 1, complex 3 reacts with triflic acid to cleave a C-S bond of the dithiolate ligand and form the triflate salt of 2. Complex 4 differs from 1 in that it undergoes an observable reaction with hydrogen in neutral or basic aqueous solution. Spectroscopic data for the hydrogen addition product are consistent with the formulation (CpMo)[sub 2]([mu]-S)[sub 2]([mu]-SH)([mu]-SCH[sub 2]CO[sub 2]Na) (7). The catalytic activity of 4 and 7 for D[sub 2]-H[sub 2]O exchange and for the hydrogenation of C=N and N=N bonds in two-phase aqueous/organic solvent systems has been studied. 30 refs., 1 fig., 4 tabs.

• OSTI ID: 5115964
• Journal Information: Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 12:12; ISSN ORGND7; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
ALKYLATION
BINDING ENERGY
CATALYSTS
CHEMICAL REACTIONS
COMPLEXES
CRYSTAL STRUCTURE
ELECTRONS
ELEMENTARY PARTICLES
ENERGY
FERMIONS
LEPTONS
LIGANDS
MOLECULAR STRUCTURE
MOLYBDENUM COMPLEXES
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
SPECTRA
SULFUR COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
VALENCE
X-RAY SPECTRA