π-Acidity and π-basicity of N-heterocyclic carbene ligands. A computational assessment

Heiko Jacobsen; Andrea Correa; Chiara Costabile; Luigi Cavallo

doi:10.1016/j.jorganchem.2006.01.026

π-Acidity and π-basicity of N-heterocyclic carbene ligands. A computational assessment

Heiko Jacobsen^*, Andrea Correa, Chiara Costabile, Luigi Cavallo

^*Corresponding author for this work

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

184 Scopus citations

Abstract

In this contribution we report on a systematic analysis of the bond between transition metals and N-heterocyclic carbene (NHC) ligands. We compare the σ and π-contributions in a series of complexes in which the formal d-electron count ranges from d⁰ to d¹⁰. Our results confirm the currently accepted idea that NHC are not pure σ-donors. In the series of complexes examined here π-contribution is 10% at least. Moreover, remarkable metal-to-ligand backdonation occurs also for d⁰ complexes, and many systems present a substantial ligand-to-metal π donation.

Original language	English (US)
Pages (from-to)	4350-4358
Number of pages	9
Journal	Journal of Organometallic Chemistry
Volume	691
Issue number	21
DOIs	https://doi.org/10.1016/j.jorganchem.2006.01.026
State	Published - Oct 15 2006
Externally published	Yes

Keywords

Carbene ligands
DFT calculations
N-Heterocylic ligands
Transition metal complexes

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.jorganchem.2006.01.026

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title = "π-Acidity and π-basicity of N-heterocyclic carbene ligands. A computational assessment",

abstract = "In this contribution we report on a systematic analysis of the bond between transition metals and N-heterocyclic carbene (NHC) ligands. We compare the σ and π-contributions in a series of complexes in which the formal d-electron count ranges from d0 to d10. Our results confirm the currently accepted idea that NHC are not pure σ-donors. In the series of complexes examined here π-contribution is 10% at least. Moreover, remarkable metal-to-ligand backdonation occurs also for d0 complexes, and many systems present a substantial ligand-to-metal π donation.",

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T1 - π-Acidity and π-basicity of N-heterocyclic carbene ligands. A computational assessment

AU - Jacobsen, Heiko

AU - Correa, Andrea

AU - Costabile, Chiara

AU - Cavallo, Luigi

PY - 2006/10/15

Y1 - 2006/10/15

N2 - In this contribution we report on a systematic analysis of the bond between transition metals and N-heterocyclic carbene (NHC) ligands. We compare the σ and π-contributions in a series of complexes in which the formal d-electron count ranges from d0 to d10. Our results confirm the currently accepted idea that NHC are not pure σ-donors. In the series of complexes examined here π-contribution is 10% at least. Moreover, remarkable metal-to-ligand backdonation occurs also for d0 complexes, and many systems present a substantial ligand-to-metal π donation.

AB - In this contribution we report on a systematic analysis of the bond between transition metals and N-heterocyclic carbene (NHC) ligands. We compare the σ and π-contributions in a series of complexes in which the formal d-electron count ranges from d0 to d10. Our results confirm the currently accepted idea that NHC are not pure σ-donors. In the series of complexes examined here π-contribution is 10% at least. Moreover, remarkable metal-to-ligand backdonation occurs also for d0 complexes, and many systems present a substantial ligand-to-metal π donation.

KW - Carbene ligands

KW - DFT calculations

KW - N-Heterocylic ligands

KW - Transition metal complexes

UR - http://www.scopus.com/inward/record.url?scp=33748743894&partnerID=8YFLogxK

U2 - 10.1016/j.jorganchem.2006.01.026

DO - 10.1016/j.jorganchem.2006.01.026

M3 - Article

AN - SCOPUS:33748743894

SN - 0022-328X

VL - 691

SP - 4350

EP - 4358

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 21

ER -

π-Acidity and π-basicity of N-heterocyclic carbene ligands. A computational assessment

Abstract

Keywords

ASJC Scopus subject areas

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