Migratory aptitude of hydride and methyl toward carbon monoxide, thiocarbonyl, and carbene in RMn(CO)/sub 4/XY (XY = CO, CS, CH/sub 2/; R = H, CH/sub 3/). A theoretical study by the Hartree-Fock-Slater transition-state method
Journal Article
·
· J. Am. Chem. Soc.; (United States)
A theoretical study based on the Hartree-Fock-Slater method has been carried out on the intramolecular migration of hydride and methyl toward CO, CS and CH/sub 2/ in RMn(CO)/sub 4/XY, (R = H, CH/sub 3/; XY = CO, CS, CH/sub 2/). The elusive hydride migration reaction to CO with a calculated enthalpy of ..delta.. H/sub 4/ = 159 kJ mol/sup -1/ was found to be considerably more endothermic than the corresponding methyl migration (..delta.. H/sub 5/ = 75 kJ mol/sup -1/) as well as the migrations of H and CH/sub 3/ to CS with calculated enthalpies of ..delta.. H/sub 6b/ = 71 kJ mol/sup -1/ and ..delta.. H/sub 6a/ = 20 kJ mol/sup -1/, respectively. Exploratory calculations along the paths of the four migratory reactions revealed only minor activation barriers. The hydride and methyl migrations to CH/sub 2/ with ..delta.. H/sub 7b/ = -113 kJ mol/sup -1/ and ..delta.. H/sub 7a/ = -71 kJ mol/sup -1/ were both found to be exothermic processes. 24 references, 4 figures, 2 tables.
- Research Organization:
- Univ. of Calgary, Alberta
- OSTI ID:
- 5815455
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:4; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALKYL RADICALS
CARBENES
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLS
CHALCOGENIDES
CHEMICAL REACTIONS
COMPLEXES
DATA
ENTHALPY
HARTREE-FOCK METHOD
HYDRIDES
HYDROGEN COMPOUNDS
INFORMATION
MANGANESE COMPLEXES
MATHEMATICAL MODELS
MECHANICS
METHYL RADICALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PHYSICAL PROPERTIES
QUANTUM MECHANICS
RADICALS
SULFUR COMPOUNDS
THEORETICAL DATA
THERMODYNAMIC PROPERTIES
TRANSITION ELEMENT COMPLEXES
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALKYL RADICALS
CARBENES
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLS
CHALCOGENIDES
CHEMICAL REACTIONS
COMPLEXES
DATA
ENTHALPY
HARTREE-FOCK METHOD
HYDRIDES
HYDROGEN COMPOUNDS
INFORMATION
MANGANESE COMPLEXES
MATHEMATICAL MODELS
MECHANICS
METHYL RADICALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PHYSICAL PROPERTIES
QUANTUM MECHANICS
RADICALS
SULFUR COMPOUNDS
THEORETICAL DATA
THERMODYNAMIC PROPERTIES
TRANSITION ELEMENT COMPLEXES