Study of fundamental reaction pathways for transition metal alkyl complexes. I. The reaction of a nickel methyl complex with alkynes. II. The mechanism of aldehyde formation in the reaction of a molybdenum hydride with molybdenum alkyls
This study reports the rapid reaction under mild conditions of internal or terminal alkynes with methyl(acetylacetonato) (triphenylphosphine) nickel (1) in either aromatic or ether solvents. In all cases vinylnickel products are formed by insertion of the alkyne into the nickel-methyl bond. In order to investigate the stereochemistry of the initial insertion, a x-ray diffraction study of the reaction of (1) with diphenylacetylene was carried out. This showed that the vinylnickel complex formed by overall trans insertion was the product of the reaction. The reaction of CpMo(CO)/sub 3/H with CpMo(CO)/sub 3/R (2, R = CH/sub 3/, C/sub 2/H/sub 5/) at 50/sup 0/C in THF gives the aldehyde RCHO and the dimers (CpMo(CO)/sub 3/)/sub 2/ (3a) and (CpMo(CO)/sub 2/)/sub 2/ (4a). Labeling one of the reactants with a methylcyclopentadienyl ligand it was possible to show that the mixed dimers MeCpMo(CO)/sub 3/-(CO)/sub 3/MoCp (3b) and MeCPMO(CO)/sub 2/ = (CO)/sub 2/MoCp (4b) are the predominant kinetic products of the reaction. A mechanism is proposed.
- Research Organization:
- California Univ., Berkeley (USA). Lawrence Berkeley Lab.
- DOE Contract Number:
- W-7405-ENG-48
- OSTI ID:
- 7063106
- Report Number(s):
- LBL-11697
- Resource Relation:
- Other Information: Thesis
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ALKYNES
CHEMICAL REACTIONS
MOLYBDENUM COMPLEXES
NICKEL COMPLEXES
CARBONYLS
CHEMICAL REACTION KINETICS
MOLYBDENUM HYDRIDES
STEREOCHEMISTRY
COMPLEXES
HYDRIDES
HYDROCARBONS
HYDROGEN COMPOUNDS
KINETICS
MOLYBDENUM COMPOUNDS
ORGANIC COMPOUNDS
REACTION KINETICS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties