Organometallic chemistry of weakly solvated transition metal cations. Final report, August 1, 1981-July 31, 1984
The catalytic chemistry of a number of weakly solvated transition metal cations have been studied. Several of these appear to be versatile catalysts for the linear polymerization, the linear and cyclic oligomerization and the rearrangement of a wide range of olefinic substrates as well as, the rearrangement of strained-ring compounds. These diverse catalytic reactions have been shown to go through a common mechanistic pathway involving the initial heterolytic cleavage of either the C-C ..pi..-bond of the olefin or the strained C-C sigma-bond of the ring compound to generate incipient carbocationic intermediates. We have discovered that cationic, tertiary phosphine complexes of Pd(II) catalyze the copolymerization of carbon monoxide with olefins under unusually mild conditions. Our studies indicate that the products arise through a mechanism involving a single mode of stepwise chain growth, and that it is possible to control the molecular weight distribution of the copolymer by a rational choice of solvents. Finally, we have discovered that tertiary phosphine complexes of Rh(I) catalyze the cooligomerization of carbon monoxide with olefins to polyketones and polyketoesters. Again, the mechanism involves a single mode of chain growth and the product distribution can be regulated by proper choice of solvents.
- Research Organization:
- Pennsylvania State Univ., University Park (USA)
- DOE Contract Number:
- AC02-81ER10992
- OSTI ID:
- 5340741
- Report Number(s):
- DOE/ER/10992-2; ON: DE84006987
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
ALKENES
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CATALYSTS
CATALYTIC EFFECTS
CHALCOGENIDES
CHEMICAL REACTIONS
COMPLEXES
HYDROCARBONS
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PALLADIUM COMPLEXES
PHOSPHINES
PHOSPHORUS COMPOUNDS
POLYMERIZATION
RHODIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES