Detail of "13601-24-6"

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Molecular orbital study of methyl migration in methylpentacarbonylmanganese(I)

Molecular orbital study of methyl migration in methylpentacarbonylmanganese(I). Axe, Frank U.; Marynick, Dennis S. (Dep. Chem., Univ. Texas, Arlington, TX 76019-0065, USA). Organometallics, 6(3), 572-80 (English) 1987. CODEN: ORGND7. ISSN: 0276-7333. DOCUMENT TYPE: Journal CA Section: 29 (Organometallic and Organometalloidal Compounds) Section cross-reference(s): 22 Approx. PRDDO calcns. and ab initio Hartree-Fock calcns. using a large basis set are used to study the nature of Me migration in MeMn(CO)5 (I). Geometries are detd. at the PRDDO level, while energetics were evaluated by ab initio theory. The optimized geometry of the transition state is obtained for the 1st time. The calcd. barrier for the closed-shell Me migration to give AcMn(CO)4 is +17 kcal/mol. The coordinatively unsatd. intermediate, which is the kinetic product of Me migration, is 10 kcal/mol less stable than the 6-coordinate Me complex. The geometries and electronic structure of the transition state and the kinetic product are discussed in relation to their possible interaction with solvent and Lewis acids. The potential for the kinetic product, which is a local min., to isomerize to other favorable conformations was studied.There are some commonly used reagents with their cas registry numbers 13601-24-6 and 13963-91-2 in this article. In-plane bending of the acyl group was relatively easy, and another conformation of the acyl intermediate was 4 kcal/mol more stable than the kinetic product. Also, a h2 conformation was 11 kcal/mol more stable than the kinetic product. The overall electronic energy difference for I carbonylation to AcMn(CO)5 is -8 kcal/mol. Localized MO's (LMO's) are used to examine qual. the bonding present during the migration sequence. The transition-state valence structure is very acyl-like in character. LMO's of the h2 species indicate that the metal-O bond is predominantly O lone pair-like, and that the metallacycle formed is highly strained. .