Theoretical study of the activation of alkane C-H and C-C bonds by different transition metals

Journal Article · Tue Jan 15 23:00:00 EST 1991 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00002a007· OSTI ID:5201367

Blomberg, M R.A.; Siegbahn, P E.M.; Nagashima, Umpei; Wennerberg, J ^[1]

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1. Univ. of Stockholm (Sweden)

The activation of C-H and C-C bonds by different transition metal atoms has been studied using quantum chemical methods including electron correlation. The metals studied are iron, cobalt, nickel, rhodium, and palladium. A general result for all these metals is that the barrier for C-C insertion is found to be 14-20 kcal/mol higher than the barrier for C-H insertion. This can be explained by the difference in directionality between bonds to methyl groups and to hydrogen atoms. The size of the activation barrier is similar among transition metals in the same row but is considerably lower for the second-row metals than for the first-row metals studied here. This latter result follows from the more efficient sd-hybridization obtained for second-row metals, which in turn follows from the more similar size of the nd and (n + 1)s orbitals for these atoms. The differences in the atomic spectra between first- and second-row metals also play a part in making the barrier for second-row metals lower.

• OSTI ID: 5201367
• Journal Information: Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 113:2; ISSN 0002-7863; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKANES
CHEMICAL ACTIVATION
COBALT
CORRELATIONS
DATA
ELECTRON CORRELATION
ELEMENTS
ETHANE
HYDROCARBONS
INFORMATION
IRON
METALS
NICKEL
NUMERICAL DATA
ORGANIC COMPOUNDS
PALLADIUM
PLATINUM METALS
RHODIUM
THEORETICAL DATA
TRANSITION ELEMENTS