Activation of C-H bonds in saturated hydrocarbons on photolysis of (eta/sup 5/-C/sub 5/Me/sub 5/)(PMe/sub 3/)IrH/sub 2/. Relative rates of reaction of the intermediate with different types of C-H bonds and functionalization of the metal-bound alkyl groups
- Univ. of California, Berkeley
Irradiation of (eta/sup 5/-pentamethylcyclopenta-dienyl)(trimethyl phosphine) dehydroiridium (eta/sup 5/-C/sub 5/Me/sub 5/)(PMe/sub 3/)IrH/sub 2/ in saturated hydrocarbons using a 500 W Oriel focused-beam mercury lamp leads to extrusion of hydrogen and production of the hydrido alkyl iridium complexes (----HRIr). Competition experiments were used to measure relative rates at which the intermediate formed on hydrogen loss reacts with different types of C-H bonds. Relative to cyclohexane (1), these rates are: benzene (4), cyclopropane (2.65), cyclopentane (1.6), neopentane (1.14), cyclodecane (.23), and cyclooctane (.09). Reductive elimination of hydrocarbon occurs at elevated temperature, regenerating the intermediate, which may then react with another hydrocarbon acting as solvent. The factors which presumed to influence the rates of reaction of transition-metal complexes with saturated C-H bonds are discussed.
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 5614725
- Journal Information:
- J. Am. Chem. Soc.; (United States), Vol. 105:12
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
2-2-DIMETHYLPROPANE
EXCITATION
NMR SPECTRA
BENZENE
CYCLOHEXANE
CHEMICAL ACTIVATION
CHEMICAL REACTION KINETICS
COMPARATIVE EVALUATIONS
DIENES
EXPERIMENTAL DATA
IRIDIUM HYDRIDES
ORGANIC PHOSPHORUS COMPOUNDS
ORGANIC SOLVENTS
ORGANOMETALLIC COMPOUNDS
PHOTOIONIZATION
REACTION INTERMEDIATES
STRUCTURAL CHEMICAL ANALYSIS
ALKANES
AROMATICS
CYCLOALKANES
DATA
ENERGY-LEVEL TRANSITIONS
HYDRIDES
HYDROCARBONS
HYDROGEN COMPOUNDS
INFORMATION
IONIZATION
IRIDIUM COMPOUNDS
KINETICS
NUMERICAL DATA
ORGANIC COMPOUNDS
POLYENES
REACTION KINETICS
SOLVENTS
SPECTRA
TRANSITION ELEMENT COMPOUNDS
400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)
400201 - Chemical & Physicochemical Properties