First C-C bond formation in the Pauson-Khand reaction: Influence of carbon-carbon triple bond polarization on regiochemistry. A density functional theory study

Theodorus J M de Bruin, Carine Michel, K. Vékey, Andrew E. Greene, Yves Gimbert, Anne Milet

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

The influence of carbon-carbon triple bond polarization on the regiochemistry of the Pauson-Khand reaction has been studied with the B3LYP functional. The regiochemistry determining step of this reaction, i.e., olefin insertion leading to cobaltacycle formation, has been examined with ethylene as the olefin and propyne, methyl 2-butynoate, and methyl propiolate as the acetylenes. From this study, it has been concluded that, in absence of overwhelming steric effects of an acetylene substituent, the regiochemistry is influenced by the polarization of the acetylenic bond, which arises from the different substituents. The initial C-C bond is preferentially formed with the acetylenic carbon that has the greater electron density: with propyne, this leads to a cyclopentenone having the methyl group in the α-position; with methyl 2-butynoate, to a cyclopentenone with the CO2Me in the β-position; with methyl propiolate, which is virtually unpolarized in the complex, to a cyclopentenone with the CO2Me in the α-position (a result of steric effects). These theoretical results are concordant with those observed experimentally with norbornene. The question of axial versus equatorial reactive positions for the coordinated olefin is also addressed and a kinetic simulation is presented.

Original languageEnglish
Pages (from-to)4281-4288
Number of pages8
JournalJournal of Organometallic Chemistry
Volume691
Issue number20
DOIs
Publication statusPublished - Oct 1 2006

Fingerprint

Alkenes
Olefins
Density functional theory
Carbon
Acetylene
Polarization
density functional theory
alkenes
carbon
polarization
acetylene
Alkynes
Carrier concentration
Ethylene
Electrons
insertion
Kinetics
ethylene
cyclopentenone
kinetics

Keywords

  • DFT studies
  • Olefin insertion
  • Pauson-Khand reaction
  • Triple-bond polarization

ASJC Scopus subject areas

  • Chemical Engineering (miscellaneous)
  • Materials Science (miscellaneous)
  • Materials Chemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Biochemistry

Cite this

First C-C bond formation in the Pauson-Khand reaction : Influence of carbon-carbon triple bond polarization on regiochemistry. A density functional theory study. / de Bruin, Theodorus J M; Michel, Carine; Vékey, K.; Greene, Andrew E.; Gimbert, Yves; Milet, Anne.

In: Journal of Organometallic Chemistry, Vol. 691, No. 20, 01.10.2006, p. 4281-4288.

Research output: Contribution to journalArticle

de Bruin, Theodorus J M ; Michel, Carine ; Vékey, K. ; Greene, Andrew E. ; Gimbert, Yves ; Milet, Anne. / First C-C bond formation in the Pauson-Khand reaction : Influence of carbon-carbon triple bond polarization on regiochemistry. A density functional theory study. In: Journal of Organometallic Chemistry. 2006 ; Vol. 691, No. 20. pp. 4281-4288.
@article{34e0bfc3783e4864967392e000ab9882,
title = "First C-C bond formation in the Pauson-Khand reaction: Influence of carbon-carbon triple bond polarization on regiochemistry. A density functional theory study",
abstract = "The influence of carbon-carbon triple bond polarization on the regiochemistry of the Pauson-Khand reaction has been studied with the B3LYP functional. The regiochemistry determining step of this reaction, i.e., olefin insertion leading to cobaltacycle formation, has been examined with ethylene as the olefin and propyne, methyl 2-butynoate, and methyl propiolate as the acetylenes. From this study, it has been concluded that, in absence of overwhelming steric effects of an acetylene substituent, the regiochemistry is influenced by the polarization of the acetylenic bond, which arises from the different substituents. The initial C-C bond is preferentially formed with the acetylenic carbon that has the greater electron density: with propyne, this leads to a cyclopentenone having the methyl group in the α-position; with methyl 2-butynoate, to a cyclopentenone with the CO2Me in the β-position; with methyl propiolate, which is virtually unpolarized in the complex, to a cyclopentenone with the CO2Me in the α-position (a result of steric effects). These theoretical results are concordant with those observed experimentally with norbornene. The question of axial versus equatorial reactive positions for the coordinated olefin is also addressed and a kinetic simulation is presented.",
keywords = "DFT studies, Olefin insertion, Pauson-Khand reaction, Triple-bond polarization",
author = "{de Bruin}, {Theodorus J M} and Carine Michel and K. V{\'e}key and Greene, {Andrew E.} and Yves Gimbert and Anne Milet",
year = "2006",
month = "10",
day = "1",
doi = "10.1016/j.jorganchem.2006.07.002",
language = "English",
volume = "691",
pages = "4281--4288",
journal = "Journal of Organometallic Chemistry",
issn = "0022-328X",
publisher = "Elsevier",
number = "20",

}

TY - JOUR

T1 - First C-C bond formation in the Pauson-Khand reaction

T2 - Influence of carbon-carbon triple bond polarization on regiochemistry. A density functional theory study

AU - de Bruin, Theodorus J M

AU - Michel, Carine

AU - Vékey, K.

AU - Greene, Andrew E.

AU - Gimbert, Yves

AU - Milet, Anne

PY - 2006/10/1

Y1 - 2006/10/1

N2 - The influence of carbon-carbon triple bond polarization on the regiochemistry of the Pauson-Khand reaction has been studied with the B3LYP functional. The regiochemistry determining step of this reaction, i.e., olefin insertion leading to cobaltacycle formation, has been examined with ethylene as the olefin and propyne, methyl 2-butynoate, and methyl propiolate as the acetylenes. From this study, it has been concluded that, in absence of overwhelming steric effects of an acetylene substituent, the regiochemistry is influenced by the polarization of the acetylenic bond, which arises from the different substituents. The initial C-C bond is preferentially formed with the acetylenic carbon that has the greater electron density: with propyne, this leads to a cyclopentenone having the methyl group in the α-position; with methyl 2-butynoate, to a cyclopentenone with the CO2Me in the β-position; with methyl propiolate, which is virtually unpolarized in the complex, to a cyclopentenone with the CO2Me in the α-position (a result of steric effects). These theoretical results are concordant with those observed experimentally with norbornene. The question of axial versus equatorial reactive positions for the coordinated olefin is also addressed and a kinetic simulation is presented.

AB - The influence of carbon-carbon triple bond polarization on the regiochemistry of the Pauson-Khand reaction has been studied with the B3LYP functional. The regiochemistry determining step of this reaction, i.e., olefin insertion leading to cobaltacycle formation, has been examined with ethylene as the olefin and propyne, methyl 2-butynoate, and methyl propiolate as the acetylenes. From this study, it has been concluded that, in absence of overwhelming steric effects of an acetylene substituent, the regiochemistry is influenced by the polarization of the acetylenic bond, which arises from the different substituents. The initial C-C bond is preferentially formed with the acetylenic carbon that has the greater electron density: with propyne, this leads to a cyclopentenone having the methyl group in the α-position; with methyl 2-butynoate, to a cyclopentenone with the CO2Me in the β-position; with methyl propiolate, which is virtually unpolarized in the complex, to a cyclopentenone with the CO2Me in the α-position (a result of steric effects). These theoretical results are concordant with those observed experimentally with norbornene. The question of axial versus equatorial reactive positions for the coordinated olefin is also addressed and a kinetic simulation is presented.

KW - DFT studies

KW - Olefin insertion

KW - Pauson-Khand reaction

KW - Triple-bond polarization

UR - http://www.scopus.com/inward/record.url?scp=33747883758&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33747883758&partnerID=8YFLogxK

U2 - 10.1016/j.jorganchem.2006.07.002

DO - 10.1016/j.jorganchem.2006.07.002

M3 - Article

AN - SCOPUS:33747883758

VL - 691

SP - 4281

EP - 4288

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

IS - 20

ER -