Insertion of carbon monoxide into the Sc-H bond of Cl/sub 2/ScH

Journal Article · Wed Sep 16 04:00:00 EDT 1987 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00253a008· OSTI ID:5976049

Rappe, A K

Correlated ab initio theoretical calculations at the valence double-zeta plus polarization level are used to study the insertion of carbon monoxide into a scandium-hydrogen sigma bond. The authors find a Lewis acid-Lewis base interaction between scandium and the carbon monoxide of 16.4 kcal/mol. The reaction occurs with a relatively small activation energy (..delta..E/sup double dagger/ = 23.7 kcal/mol. with respect to the Lewis acid-base complex) leading to an eta/sup 2/-formyl complex. The reaction is moderately exothermic (..delta..E = -6.1 kcal/mol with respect to the Lewis acid-base complex). The explanation for the small barrier is precisely the same as for previously studied metallo 2 + 2 reactions. The effect of polarization functions and electron correlation on the position of the transition state and exothermicity of the reaction were also studied.

• Research Organization: Colorado State Univ., Fort Collins
• OSTI ID: 5976049
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:19; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ACTIVATION ENERGY
BASES
BOND ANGLE
BOND LENGTHS
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CHALCOGENIDES
CHEMICAL BONDS
CHEMICAL REACTIONS
CHLORINE COMPOUNDS
DATA
DIMENSIONS
ELECTRONIC STRUCTURE
ENERGY
HALOGEN COMPOUNDS
HYDROGEN COMPOUNDS
INFORMATION
INORGANIC ACIDS
LENGTH
LEWIS ACIDS
LEWIS BASES
MATHEMATICAL MODELS
MOLECULAR MODELS
MOLECULAR STRUCTURE
NUMERICAL DATA
OXIDES
OXYGEN COMPOUNDS
SCANDIUM COMPOUNDS
THEORETICAL DATA
TRANSITION ELEMENT COMPOUNDS
VALENCE