Structure and bonding in binuclear metal carbonyls from the analysis of domain averaged fermi holes. I. Fe2(CO)9 and Co 2(CO)8

Robert Ponec, G. Lendvay, Joaquin Chaves

Research output: Contribution to journalArticle

55 Citations (Scopus)

Abstract

The nature of the bonding in the above carbonyls was studied using the analysis of domain averaged Fermi holes (DAFH). The results straightforwardly confirm the conclusions of earlier theoretical studies in which the existence of direct metal-metal bond, anticipated for the above carbonyls on the basis of 18-electron rule, was questioned. In addition to indicating the lack of direct metal-metal bond, the DAFH analysis also allowed to characterize the nature of the electron pairs involved in the bonding of the bridging ligands. The analysis has shown that because the number of available electron pairs is not sufficient for the formation of ordinary localized 2c-2e bonds between terminal M(CO) 3 fragments and the bridging ligands, the bonding in both carbonyls exhibits typical features of electron deficiency and one bonding electron pair is effectively involved in multicenter 3c-2e bonding. Because of the symmetry of the complexes the bridging ligands are not distinguishable and all M-C-M bridges have a partial 3c-2e nature via resonance of the localized structures.

Original languageEnglish
Pages (from-to)1387-1398
Number of pages12
JournalJournal of Computational Chemistry
Volume29
Issue number9
DOIs
Publication statusPublished - Jul 15 2008

Fingerprint

Carbon Monoxide
Metals
Electron
Electrons
Ligands
Localized Structures
Fragment
nonacarbonyl diiron
Sufficient
Partial
Symmetry

Keywords

  • Bonding in metal carbonyls
  • Chemical bond
  • Domain averaged Fermi holes

ASJC Scopus subject areas

  • Chemistry(all)
  • Safety, Risk, Reliability and Quality

Cite this

Structure and bonding in binuclear metal carbonyls from the analysis of domain averaged fermi holes. I. Fe2(CO)9 and Co 2(CO)8 . / Ponec, Robert; Lendvay, G.; Chaves, Joaquin.

In: Journal of Computational Chemistry, Vol. 29, No. 9, 15.07.2008, p. 1387-1398.

Research output: Contribution to journalArticle

@article{8f6734ea6f2a457593e2c4ebbc879ad0,
title = "Structure and bonding in binuclear metal carbonyls from the analysis of domain averaged fermi holes. I. Fe2(CO)9 and Co 2(CO)8",
abstract = "The nature of the bonding in the above carbonyls was studied using the analysis of domain averaged Fermi holes (DAFH). The results straightforwardly confirm the conclusions of earlier theoretical studies in which the existence of direct metal-metal bond, anticipated for the above carbonyls on the basis of 18-electron rule, was questioned. In addition to indicating the lack of direct metal-metal bond, the DAFH analysis also allowed to characterize the nature of the electron pairs involved in the bonding of the bridging ligands. The analysis has shown that because the number of available electron pairs is not sufficient for the formation of ordinary localized 2c-2e bonds between terminal M(CO) 3 fragments and the bridging ligands, the bonding in both carbonyls exhibits typical features of electron deficiency and one bonding electron pair is effectively involved in multicenter 3c-2e bonding. Because of the symmetry of the complexes the bridging ligands are not distinguishable and all M-C-M bridges have a partial 3c-2e nature via resonance of the localized structures.",
keywords = "Bonding in metal carbonyls, Chemical bond, Domain averaged Fermi holes",
author = "Robert Ponec and G. Lendvay and Joaquin Chaves",
year = "2008",
month = "7",
day = "15",
doi = "10.1002/jcc.20894",
language = "English",
volume = "29",
pages = "1387--1398",
journal = "Journal of Computational Chemistry",
issn = "0192-8651",
publisher = "John Wiley and Sons Inc.",
number = "9",

}

TY - JOUR

T1 - Structure and bonding in binuclear metal carbonyls from the analysis of domain averaged fermi holes. I. Fe2(CO)9 and Co 2(CO)8

AU - Ponec, Robert

AU - Lendvay, G.

AU - Chaves, Joaquin

PY - 2008/7/15

Y1 - 2008/7/15

N2 - The nature of the bonding in the above carbonyls was studied using the analysis of domain averaged Fermi holes (DAFH). The results straightforwardly confirm the conclusions of earlier theoretical studies in which the existence of direct metal-metal bond, anticipated for the above carbonyls on the basis of 18-electron rule, was questioned. In addition to indicating the lack of direct metal-metal bond, the DAFH analysis also allowed to characterize the nature of the electron pairs involved in the bonding of the bridging ligands. The analysis has shown that because the number of available electron pairs is not sufficient for the formation of ordinary localized 2c-2e bonds between terminal M(CO) 3 fragments and the bridging ligands, the bonding in both carbonyls exhibits typical features of electron deficiency and one bonding electron pair is effectively involved in multicenter 3c-2e bonding. Because of the symmetry of the complexes the bridging ligands are not distinguishable and all M-C-M bridges have a partial 3c-2e nature via resonance of the localized structures.

AB - The nature of the bonding in the above carbonyls was studied using the analysis of domain averaged Fermi holes (DAFH). The results straightforwardly confirm the conclusions of earlier theoretical studies in which the existence of direct metal-metal bond, anticipated for the above carbonyls on the basis of 18-electron rule, was questioned. In addition to indicating the lack of direct metal-metal bond, the DAFH analysis also allowed to characterize the nature of the electron pairs involved in the bonding of the bridging ligands. The analysis has shown that because the number of available electron pairs is not sufficient for the formation of ordinary localized 2c-2e bonds between terminal M(CO) 3 fragments and the bridging ligands, the bonding in both carbonyls exhibits typical features of electron deficiency and one bonding electron pair is effectively involved in multicenter 3c-2e bonding. Because of the symmetry of the complexes the bridging ligands are not distinguishable and all M-C-M bridges have a partial 3c-2e nature via resonance of the localized structures.

KW - Bonding in metal carbonyls

KW - Chemical bond

KW - Domain averaged Fermi holes

UR - http://www.scopus.com/inward/record.url?scp=44449135573&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=44449135573&partnerID=8YFLogxK

U2 - 10.1002/jcc.20894

DO - 10.1002/jcc.20894

M3 - Article

VL - 29

SP - 1387

EP - 1398

JO - Journal of Computational Chemistry

JF - Journal of Computational Chemistry

SN - 0192-8651

IS - 9

ER -