title: Hydroformylation and isomerization of allene and propyne: a density functional theory study.
abstract: The [HCo(CO)3]-catalyzed hydroformylation of allene and propyne has been investigated at the B3LYP level of density functional theory. It is found that hydroformylation of allene favors the linear anti-Markovnikov product in high regioselectivity both kinetically and thermodynamically. The origin of this regioselectivity comes from the enhanced stability of the eta3-allylic intermediate [(eta3-CH2CHCH2)Co(CO)3]. By contrast, propyne does not show any regioselectivity. The possible interconversion between allene and propyne mediated by [HCo(CO)3] has been explored.
authors.affiliation: State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, PR China.
authors.forename: Chun-Fang
authors.initials: CF
authors.lastname: Huo
authors.forename: Yong-Wang
authors.initials: YW
authors.lastname: Li
authors.forename: Matthias
authors.initials: M
authors.lastname: Beller
authors.forename: Haijun
authors.initials: H
authors.lastname: Jiao
mesh_terms: D000447:Aldehydes / Q000737:chemistry; D000466:Alkadienes / Q000737:chemistry*; D000480:Alkynes / Q000737:chemistry*; D005561:Formates / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D011789:Quantum Theory; D013237:Stereoisomerism
chemical_list: D000447:Aldehydes; D000466:Alkadienes; D000480:Alkynes; D005561:Formates; C022030:methylacetylene; C030544:formic acid; C025947:propadiene