Mo[sub 4](H)[sub 3]/(O-t-Bu)[sub 7](HNMe[sub 2]). A novel hydrido cluster of molybdenum

Journal Article · Wed Oct 20 04:00:00 EDT 1993 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00074a090· OSTI ID:5147143

Chisholm, M H; Huffman, J C; Kramer, K S; Streib, W E ^[1]

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1. Indiana Univ., Bloomington, IN (United States)

We report here on our initial studies aimed at preparing polynuclear polyhydrides of molybdenum supported by alkoxide ligands. In initial reactions between 1,2-Mo[sub 2](O-t-Bu)[sub 4](p-tolyl)[sub 2] and H[sub 2], only intractable molybdenum-containing products were formed. We were, however, able to isolate a hydrido alkoxide molybdenum cluster, namely, Mo[sub 4](H)[sub 3](O-t-Bu)[sub 7](HNMe[sub 2]) from the reaction employed. The dark brown crystalline compound Mo[sub 4](H)[sub 3](O-t-Bu)[sub 7[minus]] (HNMe[sub 2]) (1) is air sensitive and hydrocarbon soluble and is obtained by crystallization of the concentrated mother liquor generated in the reaction upon cooling to -20[degrees]C. It can be isolated in ca. 40% yield based on preparation involving 0.5-1.0 g of Mo[sub 2](p-tolyl)[sub 2](NMe[sub 2])[sub 4]. The elemental analysis, the spectroscopic data, and the crystallographic data provide uniform confirmation that we have, indeed, prepared Mo[sub 4](H)[sub 3](O-t-Bu)[sub 7](HNMe[sub 2]), the first polynuclear polyhydride of molybdenum supported by alkoxide ligands. The overall oxidation state of molybdenum has gone from +3.0 to +2.5 as a result of the reduction of an amide to an amine ligand, and the structure of the 14-electron cluster is, to our knowledge, without a precedent. It is interesting to note that in both 1 and W[sub 6](H)[sub 5](O-i-Pr)[sub 13], the hydride ligands reveal a propensity to group themselves on a triangular face, though in the latter molecule there are additional hydride ligands. 13 refs., 1 fig.

• OSTI ID: 5147143
• Journal Information: Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 115:21; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
COMPLEXES
CRYSTALLOGRAPHY
HYDRIDES
HYDROGEN COMPOUNDS
INFRARED SPECTRA
LIGANDS
MAGNETIC RESONANCE
MOLYBDENUM COMPLEXES
NUCLEAR MAGNETIC RESONANCE
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
RESONANCE
SOLID CLUSTERS
SPECTRA
SYNTHESIS
TRANSITION ELEMENT COMPLEXES