Destabilizing dπ-pπ orbital interactions and the alkylation reactions of iron(II)-thiolate complexes

Michael T. Ashby, John H. Enemark, Dennis L Lichtenberger

Research output: Contribution to journalArticle

95 Citations (Scopus)

Abstract

For CpFe(CO)2SR (1) (R = C6H4-p-Z; Z = OMe, H, Cl, CF3, NO2) the π-type interaction between formally occupied metal d orbitals and the sulfur lone pair that is principally 3p in character has been modeled with Fenske-Hall molecular orbital calculations and experimentally investigated by gas-phase photoelectron spectroscopy. A calculation for 1 (R = H) predicts that the highest occupied molecular orbital (HOMO) is metal-sulfur antibonding and largely sulfur in character. The observed HOMO ionization energies of 1 correlate with several chemical properties, including the rate of reaction of the thiolate ligand with alkyl halides. Solvent and substituent effects on the reaction rate favor a mechanism involving nucleophilic displacement of the halide by the coordinated thiolate ligand. The nucleophilicity of the coordinated thiolate ligand of 1 is related to the metal-sulfur dπ-pπ antibonding interactions.

Original languageEnglish (US)
Pages (from-to)191-197
Number of pages7
JournalInorganic Chemistry
Volume27
Issue number1
StatePublished - 1988

Fingerprint

alkylation
Alkylation
Sulfur
Molecular orbitals
sulfur
Iron
iron
orbitals
molecular orbitals
Metals
Ligands
ligands
halides
interactions
metals
Orbital calculations
Ionization potential
Carbon Monoxide
Photoelectron spectroscopy
chemical properties

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Destabilizing dπ-pπ orbital interactions and the alkylation reactions of iron(II)-thiolate complexes. / Ashby, Michael T.; Enemark, John H.; Lichtenberger, Dennis L.

In: Inorganic Chemistry, Vol. 27, No. 1, 1988, p. 191-197.

Research output: Contribution to journalArticle

@article{0fd3d3d805f141d8bbb4d0e5c29895a9,
title = "Destabilizing dπ-pπ orbital interactions and the alkylation reactions of iron(II)-thiolate complexes",
abstract = "For CpFe(CO)2SR (1) (R = C6H4-p-Z; Z = OMe, H, Cl, CF3, NO2) the π-type interaction between formally occupied metal d orbitals and the sulfur lone pair that is principally 3p in character has been modeled with Fenske-Hall molecular orbital calculations and experimentally investigated by gas-phase photoelectron spectroscopy. A calculation for 1 (R = H) predicts that the highest occupied molecular orbital (HOMO) is metal-sulfur antibonding and largely sulfur in character. The observed HOMO ionization energies of 1 correlate with several chemical properties, including the rate of reaction of the thiolate ligand with alkyl halides. Solvent and substituent effects on the reaction rate favor a mechanism involving nucleophilic displacement of the halide by the coordinated thiolate ligand. The nucleophilicity of the coordinated thiolate ligand of 1 is related to the metal-sulfur dπ-pπ antibonding interactions.",
author = "Ashby, {Michael T.} and Enemark, {John H.} and Lichtenberger, {Dennis L}",
year = "1988",
language = "English (US)",
volume = "27",
pages = "191--197",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "1",

}

TY - JOUR

T1 - Destabilizing dπ-pπ orbital interactions and the alkylation reactions of iron(II)-thiolate complexes

AU - Ashby, Michael T.

AU - Enemark, John H.

AU - Lichtenberger, Dennis L

PY - 1988

Y1 - 1988

N2 - For CpFe(CO)2SR (1) (R = C6H4-p-Z; Z = OMe, H, Cl, CF3, NO2) the π-type interaction between formally occupied metal d orbitals and the sulfur lone pair that is principally 3p in character has been modeled with Fenske-Hall molecular orbital calculations and experimentally investigated by gas-phase photoelectron spectroscopy. A calculation for 1 (R = H) predicts that the highest occupied molecular orbital (HOMO) is metal-sulfur antibonding and largely sulfur in character. The observed HOMO ionization energies of 1 correlate with several chemical properties, including the rate of reaction of the thiolate ligand with alkyl halides. Solvent and substituent effects on the reaction rate favor a mechanism involving nucleophilic displacement of the halide by the coordinated thiolate ligand. The nucleophilicity of the coordinated thiolate ligand of 1 is related to the metal-sulfur dπ-pπ antibonding interactions.

AB - For CpFe(CO)2SR (1) (R = C6H4-p-Z; Z = OMe, H, Cl, CF3, NO2) the π-type interaction between formally occupied metal d orbitals and the sulfur lone pair that is principally 3p in character has been modeled with Fenske-Hall molecular orbital calculations and experimentally investigated by gas-phase photoelectron spectroscopy. A calculation for 1 (R = H) predicts that the highest occupied molecular orbital (HOMO) is metal-sulfur antibonding and largely sulfur in character. The observed HOMO ionization energies of 1 correlate with several chemical properties, including the rate of reaction of the thiolate ligand with alkyl halides. Solvent and substituent effects on the reaction rate favor a mechanism involving nucleophilic displacement of the halide by the coordinated thiolate ligand. The nucleophilicity of the coordinated thiolate ligand of 1 is related to the metal-sulfur dπ-pπ antibonding interactions.

UR - http://www.scopus.com/inward/record.url?scp=0000423363&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000423363&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0000423363

VL - 27

SP - 191

EP - 197

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 1

ER -