Metal alkoxides. Models for metal oxides. Alkoxide ligands in early transition metal organometallic chemistry. Final technical report
Structural analogies between polynuclear metal alkoxides/metal oxoalkoxides and metal oxides have been noted, with the former providing models for the subunits within the extended networks of the latter. The presence of metal-metal bonds imposes a rigidity to alkoxide clusters in solution and the nuclearity of the cluster is maintained. The ability of alkoxide ligands to act as terminal or bridging ligands (..mu../sub 2/ and ..mu../sub 3/) and to respond to electron-deficient metal centers by ..pi.. donation, together with their ability to interconvert between these various modes of bonding allows for the uptake and release of substrate molecules. An extensive organometallic chemistry supported by alkoxide ligands is emerging. Key findings during the reporting period have been: (1) the reduction of carbon-monoxide by molybdenum and tungsten alkoxides; (2) the coupling, co-coupling and sometimes metathesis-like reactions between C-C, C-N, and M-M triple bonds supported by alkoxide ligands; (3) unusual ..beta..-hydrogen effects in alkyl ligands bonded to M/sub 2/(OR)/sub x/ centers; (4) the isolation of quadruple bonds between Mo atoms supported by RO ligands; (5) the synthesis of new hydrido-tungsten alkoxides of formula NaW/sub 2/(H)(OR)/sub 8/; and (6) the synthesis and characterization of the first examples of carbido, nitrido, imido and alkylidyne clusters of tungsten and molybdenum supported by alkoxide ligands. MO calculations employing Extended Huckel or Fenske-Hall methods have been performed on several of these cluster alkoxides and the results compared with observed spectrochemical and electrochemical data.
- Research Organization:
- Indiana Univ., Bloomington (USA). Dept. of Chemistry
- DOE Contract Number:
- AC02-80ER10639
- OSTI ID:
- 5568971
- Report Number(s):
- DOE/ER/10639-T3; ON: DE86012808
- Resource Relation:
- Other Information: Portions of this document are illegible in microfiche products
- Country of Publication:
- United States
- Language:
- English
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(Metal alkoxides: Models for metal oxides: Alkoxide ligands in early transition metal organometallic chemistry): Progress report
Metal alkoxides - models for metal oxides. 1. Preparations and structures of hexadecaalkoxytetatungsten compounds, W/sub 4/(OR)/sub 16/, where R = Me and Et, and octaoxotetraisopropoxytetrapyridinotetramolybdenum, Mo/sub 4/(O)/sub 4/(. mu. -O)/sub 2/(. mu. /sub 3/-O)/sub 2/(O-i-Pr)/sub 2/(. mu. -O-i-Pr)/sub 2/(py)/sub 4/
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ALKOXIDES
SYNTHESIS
CARBON MONOXIDE
REDUCTION
MOLYBDENUM COMPOUNDS
ORGANOMETALLIC COMPOUNDS
TUNGSTEN COMPOUNDS
ACETYLENE
AMIDES
AMMONIA
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
LIGANDS
MOLYBDENUM NITRIDES
SODIUM HYDRIDES
STRUCTURAL MODELS
TUNGSTEN CARBIDES
TUNGSTEN HYDRIDES
TUNGSTEN NITRIDES
ALKALI METAL COMPOUNDS
ALKYNES
CARBIDES
CARBON COMPOUNDS
CARBON OXIDES
CHALCOGENIDES
HYDRIDES
HYDROCARBONS
HYDROGEN COMPOUNDS
KINETICS
NITRIDES
NITROGEN COMPOUNDS
NITROGEN HYDRIDES
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PNICTIDES
REACTION KINETICS
REFRACTORY METAL COMPOUNDS
SODIUM COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)
400201 - Chemical & Physicochemical Properties