A density functional theory study of alkyl group migration in RMn(CO)5 complexes

Xianghuai Wang; Eric Weitz

doi:10.1016/j.jorganchem.2004.04.025

A density functional theory study of alkyl group migration in RMn(CO)₅ complexes

Xianghuai Wang, Eric Weitz^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

9 Scopus citations

Abstract

The kinetics of alkyl group migration in RMn(CO)₅ complexes (R=CH₃, C₂H₅ and C₃H₇) were studied. Isomers of CH₃ Mn(CO)₅ with an agostic structure, an η¹ structure, and an η² structure were found to be local minima on the system's potential energy surface. Transition states for the inter-conversion of these species were also located. The activation free energy for this migration reaction was compared with experimental data and provides insights into the important steps in the overall reaction mechanism.

Original language	English (US)
Pages (from-to)	2354-2360
Number of pages	7
Journal	Journal of Organometallic Chemistry
Volume	689
Issue number	14
DOIs	https://doi.org/10.1016/j.jorganchem.2004.04.025
State	Published - Jul 15 2004

Keywords

Alkyl manganese pentacarbonyls
Alkyl migration reaction
CO migratory insertion
Methyl manganese pentacarbonyl

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/j.jorganchem.2004.04.025

Cite this

@article{f40665cba4c34900af639ae5f1e6fb48,

title = "A density functional theory study of alkyl group migration in RMn(CO)5 complexes",

abstract = "The kinetics of alkyl group migration in RMn(CO)5 complexes (R=CH3, C2H5 and C3H7) were studied. Isomers of CH3 Mn(CO)5 with an agostic structure, an η1 structure, and an η2 structure were found to be local minima on the system's potential energy surface. Transition states for the inter-conversion of these species were also located. The activation free energy for this migration reaction was compared with experimental data and provides insights into the important steps in the overall reaction mechanism.",

keywords = "Alkyl manganese pentacarbonyls, Alkyl migration reaction, CO migratory insertion, Methyl manganese pentacarbonyl",

author = "Xianghuai Wang and Eric Weitz",

note = "Funding Information: We acknowledge support of this work by the National Science Foundation under Grant CHE97-34891.",

year = "2004",

month = jul,

day = "15",

doi = "10.1016/j.jorganchem.2004.04.025",

language = "English (US)",

volume = "689",

pages = "2354--2360",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier",

number = "14",

}

TY - JOUR

T1 - A density functional theory study of alkyl group migration in RMn(CO)5 complexes

AU - Wang, Xianghuai

AU - Weitz, Eric

N1 - Funding Information: We acknowledge support of this work by the National Science Foundation under Grant CHE97-34891.

PY - 2004/7/15

Y1 - 2004/7/15

N2 - The kinetics of alkyl group migration in RMn(CO)5 complexes (R=CH3, C2H5 and C3H7) were studied. Isomers of CH3 Mn(CO)5 with an agostic structure, an η1 structure, and an η2 structure were found to be local minima on the system's potential energy surface. Transition states for the inter-conversion of these species were also located. The activation free energy for this migration reaction was compared with experimental data and provides insights into the important steps in the overall reaction mechanism.

AB - The kinetics of alkyl group migration in RMn(CO)5 complexes (R=CH3, C2H5 and C3H7) were studied. Isomers of CH3 Mn(CO)5 with an agostic structure, an η1 structure, and an η2 structure were found to be local minima on the system's potential energy surface. Transition states for the inter-conversion of these species were also located. The activation free energy for this migration reaction was compared with experimental data and provides insights into the important steps in the overall reaction mechanism.

KW - Alkyl manganese pentacarbonyls

KW - Alkyl migration reaction

KW - CO migratory insertion

KW - Methyl manganese pentacarbonyl

UR - http://www.scopus.com/inward/record.url?scp=2942667691&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=2942667691&partnerID=8YFLogxK

U2 - 10.1016/j.jorganchem.2004.04.025

DO - 10.1016/j.jorganchem.2004.04.025

M3 - Article

AN - SCOPUS:2942667691

SN - 0022-328X

VL - 689

SP - 2354

EP - 2360

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 14

ER -