Metal alkoxides: models for metal oxides. Alkoxide ligands in early transition metal organometallic chemistry

Technical Report · Tue Jan 01 00:00:00 EST 1985

OSTI ID:5847614

Chisholm, M H

Structural analogies between polynuclear metal alkoxides and metal oxides have been noted, with the former providing models for subunits within the extended networks of the latter. An extensive organometallic chemistry supported by alkoxy ligands is emerging. Their facile interconversion between terminal and bridging positions and between sigma/sup 2/ and (sigma/sup 2/ + ..pi../sup 2/) donors allows for easy uptake and release of substrate molecules. Key reports during the 1984 to 1985 period are: (1) the cleavage of C identical with O to carbido and oxo tungsten alkoxide clusters; (2) the coupling, co-coupling, and sometimes metathesis-like reactions (M = W) between C idential with C, C identical with N and M identical with M bonds in M/sub 2/(OR)/sub 6/ compounds; (3) unusual ..beta..-hydrogen effects in dinuclear alkyl-alkoxides of molybdenum; and (4) the isolation of Mo-Mo quadruply bonded compounds supported by alkoxide ligands. Recent developments have led to general synthesis of hydridoditungsten alkoxide anions W/sub 2/(..mu..-H)(OR/sub 8//sup -/ which have been isolated as sodium salts. New nitrido and amido clusters have been discovered, Mo/sub 4/(..mu../sub 3/-N)/sub 2/(OPr/sup i/)/sub 12/ and W/sub 3/(..mu../sub 3/-NH)OPr/sup i/)/sub 10/ which may provide models for the Haber synthesis of NH/sub 3/ from N/sub 2/ and H/sub 2/.

• Research Organization: Indiana Univ., Bloomington (USA). Dept. of Chemistry
• DOE Contract Number: AC02-80ER10639
• OSTI ID: 5847614
• Report Number(s): DOE/ER/10639-T2; ON: DE85011368
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ALKOXIDES
SYNTHESIS
MOLYBDENUM COMPOUNDS
ORGANOMETALLIC COMPOUNDS
TUNGSTEN COMPOUNDS
ACETYLENE
AMIDES
AMMONIA
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
MOLYBDENUM NITRIDES
SODIUM HYDRIDES
STRUCTURAL MODELS
THEORETICAL DATA
TUNGSTEN CARBIDES
TUNGSTEN HYDRIDES
TUNGSTEN NITRIDES
ALKALI METAL COMPOUNDS
ALKYNES
CARBIDES
CARBON COMPOUNDS
DATA
HYDRIDES
HYDROCARBONS
HYDROGEN COMPOUNDS
INFORMATION
KINETICS
NITRIDES
NITROGEN COMPOUNDS
NITROGEN HYDRIDES
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PNICTIDES
REACTION KINETICS
REFRACTORY METAL COMPOUNDS
SODIUM COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)
400201 - Chemical & Physicochemical Properties