Syntheses and crystal structures of [Hg{C(PPh3) 2}2][Hg2I6] and [Cu{C(PPh 3)2}2]I and comparative theoretical study of carbene complexes [M(NHC)2] with carbone complexes [M{C(PH 3)2}2] (M = Cu+, Ag+, Au+, Zn2+

Wolfgang Petz; Bernhard Neumüller; Susanne Klein; Gernot Frenking

doi:10.1021/om200145c

Syntheses and crystal structures of [Hg{C(PPh₃) ₂}₂][Hg₂I₆] and [Cu{C(PPh ₃)₂}₂]I and comparative theoretical study of carbene complexes [M(NHC)₂] with carbone complexes [M{C(PH ₃)₂}₂] (M = Cu⁺, Ag⁺, Au⁺, Zn²⁺

Wolfgang Petz, Bernhard Neumüller, Susanne Klein, Gernot Frenking

University of Marburg

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

38 Scopus citations

Abstract

The synthesis and X-ray structure analysis of the carbodiphosphorane (CDP) complexes [Hg{C(PPh₃)₂}₂][Hg₂I ₆] and [Cu{C(PPh₃)₂}₂]I are reported. The cations [Hg{C(PPh₃)₂}₂] ²⁺ and [Cu{C(PPh₃)₂}₂]⁺ have approximately linearly coordinated metal atoms. Quantum chemical calculations of model compounds bearing N-heterocyclic carbene (NHC) ligands, [M(NHC)₂] and [M{C(PH₃)₂}₂] (M = Cu⁺, Ag⁺, Au⁺, Zn²⁺, Cd ²⁺, Hg²⁺), have been carried out at the BP86/TZ2P level. The metal-ligand bonds are very strong, and the bond dissociation energies exhibit a V-shaped trend for first-, second-, and third-row transition metals: Ag⁺ < Cu⁺ < Au⁺ and Cd²⁺ < Zn²⁺ < Hg²⁺. The investigation of the bonding situation in the complexes using an energy decomposition analysis shows that the metal-ligand bonding comes mainly from electrostatic attraction. Inspection of the orbital interactions shows that the M^q←(NHC)₂ and M^q←{C(PH₃)₂}₂ σ donation provides between 65 and 75% of the total orbital interactions ΔE _orb. The contribution of the M^q→(NHC)₂ and M^q→{C(PH₃)₂}₂ π back-donation is very weak. The nature and strength of the donor-acceptor bonds of the two-electron donor ligand NHC and the four-electron donor ligand CDP with the group 11 and group 12 metal cations are very similar.

Original language	English
Pages (from-to)	3330-3339
Number of pages	10
Journal	Organometallics
Volume	30
Issue number	12
DOIs	https://doi.org/10.1021/om200145c
State	Published - 27 Jun 2011
Externally published	Yes

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@article{d60e07b1b9ca48019cc5a9adfd235a3d,

title = "Syntheses and crystal structures of [Hg{C(PPh3) 2}2][Hg2I6] and [Cu{C(PPh 3)2}2]I and comparative theoretical study of carbene complexes [M(NHC)2] with carbone complexes [M{C(PH 3)2}2] (M = Cu+, Ag+, Au+, Zn2+",

abstract = "The synthesis and X-ray structure analysis of the carbodiphosphorane (CDP) complexes [Hg{C(PPh3)2}2][Hg2I 6] and [Cu{C(PPh3)2}2]I are reported. The cations [Hg{C(PPh3)2}2] 2+ and [Cu{C(PPh3)2}2]+ have approximately linearly coordinated metal atoms. Quantum chemical calculations of model compounds bearing N-heterocyclic carbene (NHC) ligands, [M(NHC)2] and [M{C(PH3)2}2] (M = Cu+, Ag+, Au+, Zn2+, Cd 2+, Hg2+), have been carried out at the BP86/TZ2P level. The metal-ligand bonds are very strong, and the bond dissociation energies exhibit a V-shaped trend for first-, second-, and third-row transition metals: Ag+ < Cu+ < Au+ and Cd2+ < Zn2+ < Hg2+. The investigation of the bonding situation in the complexes using an energy decomposition analysis shows that the metal-ligand bonding comes mainly from electrostatic attraction. Inspection of the orbital interactions shows that the Mq←(NHC)2 and Mq←{C(PH3)2}2 σ donation provides between 65 and 75% of the total orbital interactions ΔE orb. The contribution of the Mq→(NHC)2 and Mq→{C(PH3)2}2 π back-donation is very weak. The nature and strength of the donor-acceptor bonds of the two-electron donor ligand NHC and the four-electron donor ligand CDP with the group 11 and group 12 metal cations are very similar.",

author = "Wolfgang Petz and Bernhard Neum{\"u}ller and Susanne Klein and Gernot Frenking",

year = "2011",

month = jun,

day = "27",

doi = "10.1021/om200145c",

language = "英语",

volume = "30",

pages = "3330--3339",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "12",

}

Syntheses and crystal structures of [Hg{C(PPh₃) ₂}₂][Hg₂I₆] and [Cu{C(PPh ₃)₂}₂]I and comparative theoretical study of carbene complexes [M(NHC)₂] with carbone complexes [M{C(PH ₃)₂}₂] (M = Cu⁺, Ag⁺, Au⁺, Zn²⁺. / Petz, Wolfgang; Neumüller, Bernhard; Klein, Susanne et al.
In: Organometallics, Vol. 30, No. 12, 27.06.2011, p. 3330-3339.

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

TY - JOUR

T1 - Syntheses and crystal structures of [Hg{C(PPh3) 2}2][Hg2I6] and [Cu{C(PPh 3)2}2]I and comparative theoretical study of carbene complexes [M(NHC)2] with carbone complexes [M{C(PH 3)2}2] (M = Cu+, Ag+, Au+, Zn2+

AU - Petz, Wolfgang

AU - Neumüller, Bernhard

AU - Klein, Susanne

AU - Frenking, Gernot

PY - 2011/6/27

Y1 - 2011/6/27

N2 - The synthesis and X-ray structure analysis of the carbodiphosphorane (CDP) complexes [Hg{C(PPh3)2}2][Hg2I 6] and [Cu{C(PPh3)2}2]I are reported. The cations [Hg{C(PPh3)2}2] 2+ and [Cu{C(PPh3)2}2]+ have approximately linearly coordinated metal atoms. Quantum chemical calculations of model compounds bearing N-heterocyclic carbene (NHC) ligands, [M(NHC)2] and [M{C(PH3)2}2] (M = Cu+, Ag+, Au+, Zn2+, Cd 2+, Hg2+), have been carried out at the BP86/TZ2P level. The metal-ligand bonds are very strong, and the bond dissociation energies exhibit a V-shaped trend for first-, second-, and third-row transition metals: Ag+ < Cu+ < Au+ and Cd2+ < Zn2+ < Hg2+. The investigation of the bonding situation in the complexes using an energy decomposition analysis shows that the metal-ligand bonding comes mainly from electrostatic attraction. Inspection of the orbital interactions shows that the Mq←(NHC)2 and Mq←{C(PH3)2}2 σ donation provides between 65 and 75% of the total orbital interactions ΔE orb. The contribution of the Mq→(NHC)2 and Mq→{C(PH3)2}2 π back-donation is very weak. The nature and strength of the donor-acceptor bonds of the two-electron donor ligand NHC and the four-electron donor ligand CDP with the group 11 and group 12 metal cations are very similar.

AB - The synthesis and X-ray structure analysis of the carbodiphosphorane (CDP) complexes [Hg{C(PPh3)2}2][Hg2I 6] and [Cu{C(PPh3)2}2]I are reported. The cations [Hg{C(PPh3)2}2] 2+ and [Cu{C(PPh3)2}2]+ have approximately linearly coordinated metal atoms. Quantum chemical calculations of model compounds bearing N-heterocyclic carbene (NHC) ligands, [M(NHC)2] and [M{C(PH3)2}2] (M = Cu+, Ag+, Au+, Zn2+, Cd 2+, Hg2+), have been carried out at the BP86/TZ2P level. The metal-ligand bonds are very strong, and the bond dissociation energies exhibit a V-shaped trend for first-, second-, and third-row transition metals: Ag+ < Cu+ < Au+ and Cd2+ < Zn2+ < Hg2+. The investigation of the bonding situation in the complexes using an energy decomposition analysis shows that the metal-ligand bonding comes mainly from electrostatic attraction. Inspection of the orbital interactions shows that the Mq←(NHC)2 and Mq←{C(PH3)2}2 σ donation provides between 65 and 75% of the total orbital interactions ΔE orb. The contribution of the Mq→(NHC)2 and Mq→{C(PH3)2}2 π back-donation is very weak. The nature and strength of the donor-acceptor bonds of the two-electron donor ligand NHC and the four-electron donor ligand CDP with the group 11 and group 12 metal cations are very similar.

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U2 - 10.1021/om200145c

DO - 10.1021/om200145c

M3 - 文章

AN - SCOPUS:79959521403

SN - 0276-7333

VL - 30

SP - 3330

EP - 3339

JO - Organometallics

JF - Organometallics

IS - 12