Bonding situation in silicon complexes [(L)2(Si2)] and [(L)2(Si)] with NHC and cAAC ligands

Nicole Holzmann; Diego M. Andrada; Gernot Frenking

doi:10.1016/j.jorganchem.2015.03.029

Bonding situation in silicon complexes [(L)₂(Si₂)] and [(L)₂(Si)] with NHC and cAAC ligands

Nicole Holzmann, Diego M. Andrada, Gernot Frenking

University of Marburg

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

33 Scopus citations

Abstract

Abstract The equilibrium geometries of the silicon carbene complexes [(cAAC)₂(Si₂)], [(NHC)₂(Si₂)], [(cAAC)₂(Si)], [(NHC)₂Si] and [(NHC-CH₂-NHC)(Si)] have been calculated with gradient-corrected density functional theory (DFT) at the BP86/def2-TZVPP level of theory. A detailed bonding analysis of the five molecules was carried out with the NBO method and with the help of the EDA-NOCV method which provides a detailed and quantitative insight into the nature of the interactions between Si_n and the carbene ligands. The silicon atom in L₂Si is more strongly bonded than diatomic Si₂ in L₂Si₂. The cAAC ligands are stronger donors and stronger acceptors than NHC. The relative contribution of the cAAC ← Si_n → cAAC π-backdonation to the total orbital interactions is higher than the NHC ← Si_n → NHC π-backdonation which agrees with the general assessment that cAAC is a stronger π-acceptor than NHC. Silicon-carbene bonding in [(NHC-CH₂-NHC)(Si)] is stronger than in [(NHC)₂Si] mainly because of stronger π-backdonation but weaker than in [(cAAC)₂(Si)]. The calculated charge distribution of the NBO method agrees with the EDA-NOCV data.

Original language	English
Article number	18980
Pages (from-to)	139-148
Number of pages	10
Journal	Journal of Organometallic Chemistry
Volume	792
DOIs	https://doi.org/10.1016/j.jorganchem.2015.03.029
State	Published - 10 Aug 2015
Externally published	Yes

Keywords

Bonding analysis
Donor-acceptor complex
N-heterocyclic carbenes
Quantum chemical calculations
Silicon

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10.1016/j.jorganchem.2015.03.029

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title = "Bonding situation in silicon complexes [(L)2(Si2)] and [(L)2(Si)] with NHC and cAAC ligands",

abstract = "Abstract The equilibrium geometries of the silicon carbene complexes [(cAAC)2(Si2)], [(NHC)2(Si2)], [(cAAC)2(Si)], [(NHC)2Si] and [(NHC-CH2-NHC)(Si)] have been calculated with gradient-corrected density functional theory (DFT) at the BP86/def2-TZVPP level of theory. A detailed bonding analysis of the five molecules was carried out with the NBO method and with the help of the EDA-NOCV method which provides a detailed and quantitative insight into the nature of the interactions between Sin and the carbene ligands. The silicon atom in L2Si is more strongly bonded than diatomic Si2 in L2Si2. The cAAC ligands are stronger donors and stronger acceptors than NHC. The relative contribution of the cAAC ← Sin → cAAC π-backdonation to the total orbital interactions is higher than the NHC ← Sin → NHC π-backdonation which agrees with the general assessment that cAAC is a stronger π-acceptor than NHC. Silicon-carbene bonding in [(NHC-CH2-NHC)(Si)] is stronger than in [(NHC)2Si] mainly because of stronger π-backdonation but weaker than in [(cAAC)2(Si)]. The calculated charge distribution of the NBO method agrees with the EDA-NOCV data.",

keywords = "Bonding analysis, Donor-acceptor complex, N-heterocyclic carbenes, Quantum chemical calculations, Silicon",

author = "Nicole Holzmann and Andrada, {Diego M.} and Gernot Frenking",

note = "Publisher Copyright: {\textcopyright} 2015 Elsevier B.V.",

year = "2015",

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doi = "10.1016/j.jorganchem.2015.03.029",

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T1 - Bonding situation in silicon complexes [(L)2(Si2)] and [(L)2(Si)] with NHC and cAAC ligands

AU - Holzmann, Nicole

AU - Andrada, Diego M.

AU - Frenking, Gernot

PY - 2015/8/10

Y1 - 2015/8/10

N2 - Abstract The equilibrium geometries of the silicon carbene complexes [(cAAC)2(Si2)], [(NHC)2(Si2)], [(cAAC)2(Si)], [(NHC)2Si] and [(NHC-CH2-NHC)(Si)] have been calculated with gradient-corrected density functional theory (DFT) at the BP86/def2-TZVPP level of theory. A detailed bonding analysis of the five molecules was carried out with the NBO method and with the help of the EDA-NOCV method which provides a detailed and quantitative insight into the nature of the interactions between Sin and the carbene ligands. The silicon atom in L2Si is more strongly bonded than diatomic Si2 in L2Si2. The cAAC ligands are stronger donors and stronger acceptors than NHC. The relative contribution of the cAAC ← Sin → cAAC π-backdonation to the total orbital interactions is higher than the NHC ← Sin → NHC π-backdonation which agrees with the general assessment that cAAC is a stronger π-acceptor than NHC. Silicon-carbene bonding in [(NHC-CH2-NHC)(Si)] is stronger than in [(NHC)2Si] mainly because of stronger π-backdonation but weaker than in [(cAAC)2(Si)]. The calculated charge distribution of the NBO method agrees with the EDA-NOCV data.

AB - Abstract The equilibrium geometries of the silicon carbene complexes [(cAAC)2(Si2)], [(NHC)2(Si2)], [(cAAC)2(Si)], [(NHC)2Si] and [(NHC-CH2-NHC)(Si)] have been calculated with gradient-corrected density functional theory (DFT) at the BP86/def2-TZVPP level of theory. A detailed bonding analysis of the five molecules was carried out with the NBO method and with the help of the EDA-NOCV method which provides a detailed and quantitative insight into the nature of the interactions between Sin and the carbene ligands. The silicon atom in L2Si is more strongly bonded than diatomic Si2 in L2Si2. The cAAC ligands are stronger donors and stronger acceptors than NHC. The relative contribution of the cAAC ← Sin → cAAC π-backdonation to the total orbital interactions is higher than the NHC ← Sin → NHC π-backdonation which agrees with the general assessment that cAAC is a stronger π-acceptor than NHC. Silicon-carbene bonding in [(NHC-CH2-NHC)(Si)] is stronger than in [(NHC)2Si] mainly because of stronger π-backdonation but weaker than in [(cAAC)2(Si)]. The calculated charge distribution of the NBO method agrees with the EDA-NOCV data.

KW - Bonding analysis

KW - Donor-acceptor complex

KW - N-heterocyclic carbenes

KW - Quantum chemical calculations

KW - Silicon

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DO - 10.1016/j.jorganchem.2015.03.029

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SN - 0022-328X

VL - 792

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EP - 148

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

M1 - 18980

ER -

Bonding situation in silicon complexes [(L)₂(Si₂)] and [(L)₂(Si)] with NHC and cAAC ligands

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