Polynuclear metal hydrido alkoxides. Reactions of W[sub 4](H)[sub 2](O-i-Pr)[sub 14] and W[sub 2](H)(O-c-C[sub 5]H[sub 9])[sub 7](HNMe[sub 2]) with carbon-carbon, carbon-oxygen, and carbon-nitrogen multiple bonds
- Indiana Univ., Bloomington, IN (United States)
Reactions between the compounds [W[sub 2](H)(O-i-Pr)[sub 7]][sub 2] and W[sub 2](H)(O-c-C[sub 5]H[sub 9])[sub 7](HNMe[sub 2]) and olefins, alkynes, allene, 1,3-butadiene, ketones, and nitriles have been studied. Of the olefins, only ethene forms a kinetically persistent compound, and W[sub 2](O-c-C[sub 5]H[sub 9])[sub 7]([eta][sup 2]-C[sub 2]H[sub 4])([eta][sup 1]-C[sub 2]H[sub 5]) has been fully characterized. Other [alpha]-olefins are slowly isomerized to internal olefins, but, in the presence of added hydrogen, hydrogenolysis to give the alkane is kinetically preferred. Reactions employing allene and/or 1,3-butadiene are more complex as a result of ligand scrambling, and only the compound W[sub 2](O-c-C[sub 5]H[sub 9])[sub 8]([mu]--CH[sub 2]CCH[sub 2]) has been fully characterized. With aldehydes and ketones, insertion into the metal hydride generally proceeds to give alkoxide ligands, and the complex W[sub 2](O-c-C[sub 5]H[sub 9])[sub 8]([eta][sup 2]-O-c-C[sub 5]H[sub 8]) derived from the reaction involving W[sub 2](H)(O-c-C[sub 5]H[sub 9])[sub 7](HNMe[sub 2]) and cyclopentanone has been fully characterized. With benzophenone, an adduct is formed, which in the solid state and in solution is believed to have a terminal hydride and is formulated as W[sub 2](H)(OR)[sub 7]([eta][sup 2]-OCPh[sub 2]), an analogue of the W[sub 2]([eta][sup 1]-C[sub 2]H[sub 5])([eta][sup 2]-C[sub 2]H[sub 4]) complex. No single product from the reactions between ethyne and a W[sub 2]([mu]-H)-contaning compound has been fully characterized. 45 refs., 8 figs., 4 tabs.
- OSTI ID:
- 6766236
- Journal Information:
- Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 117:7; ISSN JACSAT; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
ADDUCTS
ALKENES
ALKOXIDES
ALKYNES
ALLENE
BUTADIENE
CHEMICAL BONDS
CHEMICAL PREPARATION
CHEMICAL REACTIONS
COMPLEXES
CRYSTAL STRUCTURE
DATA
DIENES
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
KETONES
MOLECULAR STRUCTURE
NITRILES
NMR SPECTRA
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
POLYENES
SPECTRA
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TUNGSTEN COMPLEXES