Bonding analysis of N-heterocyclic carbene tautomers and phosphine ligands in transition-metal complexes: A theoretical study

Ralf Tonner; Greta Heydenrych; Gernot Frenking

doi:10.1002/asia.200700235

Bonding analysis of N-heterocyclic carbene tautomers and phosphine ligands in transition-metal complexes: A theoretical study

Ralf Tonner, Greta Heydenrych, Gernot Frenking

University of Marburg

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

230 Scopus citations

Abstract

DFT calculations at the BP86/TZ2P level were carried out to analyze quantitatively the metal-ligand bonding in transition-metal complexes that contain imidazole (IMID), imidazol-2-ylidene (nNHC), or imidazol-4-yl-idene (aNHC). The calculated complexes are [Cl₄TM(L)] (TM = Ti, Zr, Hf), [(CO)₅TM(L)] (TM = Cr, Mo, W), [(CO)₄TM(L)] (TM = Fe, Ru, Os), and [ClTM(L)] (TM = Cu, Ag, Au). The relative energies of the free ligands increase in the order IMID < nNHC < aNHC. The energy levels of the carbon σ lone-pair orbitals suggest the trend aNHC >nNHC> IMID for the donor strength, which is in agreement with the progression of the metal-ligand bond-dissociation energy (BDE) for the three ligands for all metals of

Original language	English
Pages (from-to)	1555-1567
Number of pages	13
Journal	Chemistry - An Asian Journal
Volume	2
Issue number	12
DOIs	https://doi.org/10.1002/asia.200700235
State	Published - 2007
Externally published	Yes

Keywords

Bonding analysis
Carbenes
Density functional calculations
N-heterocyclic carbenes
Phosphine complexes

Access to Document

10.1002/asia.200700235

Cite this

@article{547ca247362d4de38da41aabf946c0d2,

title = "Bonding analysis of N-heterocyclic carbene tautomers and phosphine ligands in transition-metal complexes: A theoretical study",

abstract = "DFT calculations at the BP86/TZ2P level were carried out to analyze quantitatively the metal-ligand bonding in transition-metal complexes that contain imidazole (IMID), imidazol-2-ylidene (nNHC), or imidazol-4-yl-idene (aNHC). The calculated complexes are [Cl4TM(L)] (TM = Ti, Zr, Hf), [(CO)5TM(L)] (TM = Cr, Mo, W), [(CO)4TM(L)] (TM = Fe, Ru, Os), and [ClTM(L)] (TM = Cu, Ag, Au). The relative energies of the free ligands increase in the order IMID < nNHC < aNHC. The energy levels of the carbon σ lone-pair orbitals suggest the trend aNHC >nNHC> IMID for the donor strength, which is in agreement with the progression of the metal-ligand bond-dissociation energy (BDE) for the three ligands for all metals of",

keywords = "Bonding analysis, Carbenes, Density functional calculations, N-heterocyclic carbenes, Phosphine complexes",

author = "Ralf Tonner and Greta Heydenrych and Gernot Frenking",

year = "2007",

doi = "10.1002/asia.200700235",

language = "英语",

volume = "2",

pages = "1555--1567",

journal = "Chemistry - An Asian Journal",

issn = "1861-4728",

publisher = "John Wiley and Sons Ltd",

number = "12",

}

TY - JOUR

T1 - Bonding analysis of N-heterocyclic carbene tautomers and phosphine ligands in transition-metal complexes

T2 - A theoretical study

AU - Tonner, Ralf

AU - Heydenrych, Greta

AU - Frenking, Gernot

PY - 2007

Y1 - 2007

N2 - DFT calculations at the BP86/TZ2P level were carried out to analyze quantitatively the metal-ligand bonding in transition-metal complexes that contain imidazole (IMID), imidazol-2-ylidene (nNHC), or imidazol-4-yl-idene (aNHC). The calculated complexes are [Cl4TM(L)] (TM = Ti, Zr, Hf), [(CO)5TM(L)] (TM = Cr, Mo, W), [(CO)4TM(L)] (TM = Fe, Ru, Os), and [ClTM(L)] (TM = Cu, Ag, Au). The relative energies of the free ligands increase in the order IMID < nNHC < aNHC. The energy levels of the carbon σ lone-pair orbitals suggest the trend aNHC >nNHC> IMID for the donor strength, which is in agreement with the progression of the metal-ligand bond-dissociation energy (BDE) for the three ligands for all metals of

AB - DFT calculations at the BP86/TZ2P level were carried out to analyze quantitatively the metal-ligand bonding in transition-metal complexes that contain imidazole (IMID), imidazol-2-ylidene (nNHC), or imidazol-4-yl-idene (aNHC). The calculated complexes are [Cl4TM(L)] (TM = Ti, Zr, Hf), [(CO)5TM(L)] (TM = Cr, Mo, W), [(CO)4TM(L)] (TM = Fe, Ru, Os), and [ClTM(L)] (TM = Cu, Ag, Au). The relative energies of the free ligands increase in the order IMID < nNHC < aNHC. The energy levels of the carbon σ lone-pair orbitals suggest the trend aNHC >nNHC> IMID for the donor strength, which is in agreement with the progression of the metal-ligand bond-dissociation energy (BDE) for the three ligands for all metals of

KW - Bonding analysis

KW - Carbenes

KW - Density functional calculations

KW - N-heterocyclic carbenes

KW - Phosphine complexes

UR - http://www.scopus.com/inward/record.url?scp=36949026707&partnerID=8YFLogxK

U2 - 10.1002/asia.200700235

DO - 10.1002/asia.200700235

M3 - 文章

AN - SCOPUS:36949026707

SN - 1861-4728

VL - 2

SP - 1555

EP - 1567

JO - Chemistry - An Asian Journal

JF - Chemistry - An Asian Journal

IS - 12

ER -

Bonding analysis of N-heterocyclic carbene tautomers and phosphine ligands in transition-metal complexes: A theoretical study

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

Cite this