N-heterocyclic germylenes: structural characterisation of some heavy analogues of the ubiquitous N-heterocyclic carbenes

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Abstract

The X-ray crystal structures of three N-heterocyclic germylenes (NHGes) have been elucidated including the previously unknown 1,3-bis(2,6-dimethylphenyl)diazagermol-2-ylidene (1). In addition, the X-ray crystal structures of the previously synthesised 1,3-bis(2,4,6-trimethylphenyl)diazagermol-2-ylidene (2) and 1,3-bis(2,6-diisopropylphenyl)diazagermol-2-ylidene (3) are also reported. The discrete molecular structures of compounds 1 to 3 are comparable, with Ge-N bond lengths in the range 1.835-1.875 Å, while the N-Ge-N bond angles range between 83.6 and 85.2°. Compound 2 was compared to the analogous N-heterocyclic carbene species, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes). The major geometrical difference observed, as expected, was the bond angle around the divalent group 14 atom. The N-Ge-N bond angle was 83.6° for compound 2 versus the N-C-N bond angle of 101.4° for IMes. The Sn equivalent of (1), 1,3-bis(2,6-dimethylphenyl)diazastannol-2-ylidene (4), has also been synthesised and its crystal structure is reported here. In order to test their suitability as ligands, compounds 1 to 3 were reacted with a wide range of transition metal complexes. No NHGes containing metal complexes were observed. In all cases the NHGe either degraded or gave no reaction.
LanguageEnglish
Article number9178371
Number of pages8
JournalHeteroatom Chemistry
Volume2019
DOIs
Publication statusPublished - 23 Jan 2019

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Crystal structure
Coordination Complexes
X rays
Bond length
Molecular structure
Transition metals
Ligands
Atoms
carbene
1,3-bis-(2,4,6-trimethylphenyl)imidazol-2-ylidene

Keywords

  • N-heterocyclic germylenes
  • crystal structure
  • X-ray

Cite this

@article{398313b4772646da805ef1b1c6da34a0,
title = "N-heterocyclic germylenes: structural characterisation of some heavy analogues of the ubiquitous N-heterocyclic carbenes",
abstract = "The X-ray crystal structures of three N-heterocyclic germylenes (NHGes) have been elucidated including the previously unknown 1,3-bis(2,6-dimethylphenyl)diazagermol-2-ylidene (1). In addition, the X-ray crystal structures of the previously synthesised 1,3-bis(2,4,6-trimethylphenyl)diazagermol-2-ylidene (2) and 1,3-bis(2,6-diisopropylphenyl)diazagermol-2-ylidene (3) are also reported. The discrete molecular structures of compounds 1 to 3 are comparable, with Ge-N bond lengths in the range 1.835-1.875 {\AA}, while the N-Ge-N bond angles range between 83.6 and 85.2°. Compound 2 was compared to the analogous N-heterocyclic carbene species, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes). The major geometrical difference observed, as expected, was the bond angle around the divalent group 14 atom. The N-Ge-N bond angle was 83.6° for compound 2 versus the N-C-N bond angle of 101.4° for IMes. The Sn equivalent of (1), 1,3-bis(2,6-dimethylphenyl)diazastannol-2-ylidene (4), has also been synthesised and its crystal structure is reported here. In order to test their suitability as ligands, compounds 1 to 3 were reacted with a wide range of transition metal complexes. No NHGes containing metal complexes were observed. In all cases the NHGe either degraded or gave no reaction.",
keywords = "N-heterocyclic germylenes, crystal structure, X-ray",
author = "Dodds, {Christopher A.} and Kennedy, {Alan R.} and Spicer, {Mark D.}",
year = "2019",
month = "1",
day = "23",
doi = "10.1155/2019/9178371",
language = "English",
volume = "2019",
journal = "Heteroatom Chemistry",
issn = "1042-7163",

}

TY - JOUR

T1 - N-heterocyclic germylenes

T2 - Heteroatom Chemistry

AU - Dodds, Christopher A.

AU - Kennedy, Alan R.

AU - Spicer, Mark D.

PY - 2019/1/23

Y1 - 2019/1/23

N2 - The X-ray crystal structures of three N-heterocyclic germylenes (NHGes) have been elucidated including the previously unknown 1,3-bis(2,6-dimethylphenyl)diazagermol-2-ylidene (1). In addition, the X-ray crystal structures of the previously synthesised 1,3-bis(2,4,6-trimethylphenyl)diazagermol-2-ylidene (2) and 1,3-bis(2,6-diisopropylphenyl)diazagermol-2-ylidene (3) are also reported. The discrete molecular structures of compounds 1 to 3 are comparable, with Ge-N bond lengths in the range 1.835-1.875 Å, while the N-Ge-N bond angles range between 83.6 and 85.2°. Compound 2 was compared to the analogous N-heterocyclic carbene species, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes). The major geometrical difference observed, as expected, was the bond angle around the divalent group 14 atom. The N-Ge-N bond angle was 83.6° for compound 2 versus the N-C-N bond angle of 101.4° for IMes. The Sn equivalent of (1), 1,3-bis(2,6-dimethylphenyl)diazastannol-2-ylidene (4), has also been synthesised and its crystal structure is reported here. In order to test their suitability as ligands, compounds 1 to 3 were reacted with a wide range of transition metal complexes. No NHGes containing metal complexes were observed. In all cases the NHGe either degraded or gave no reaction.

AB - The X-ray crystal structures of three N-heterocyclic germylenes (NHGes) have been elucidated including the previously unknown 1,3-bis(2,6-dimethylphenyl)diazagermol-2-ylidene (1). In addition, the X-ray crystal structures of the previously synthesised 1,3-bis(2,4,6-trimethylphenyl)diazagermol-2-ylidene (2) and 1,3-bis(2,6-diisopropylphenyl)diazagermol-2-ylidene (3) are also reported. The discrete molecular structures of compounds 1 to 3 are comparable, with Ge-N bond lengths in the range 1.835-1.875 Å, while the N-Ge-N bond angles range between 83.6 and 85.2°. Compound 2 was compared to the analogous N-heterocyclic carbene species, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes). The major geometrical difference observed, as expected, was the bond angle around the divalent group 14 atom. The N-Ge-N bond angle was 83.6° for compound 2 versus the N-C-N bond angle of 101.4° for IMes. The Sn equivalent of (1), 1,3-bis(2,6-dimethylphenyl)diazastannol-2-ylidene (4), has also been synthesised and its crystal structure is reported here. In order to test their suitability as ligands, compounds 1 to 3 were reacted with a wide range of transition metal complexes. No NHGes containing metal complexes were observed. In all cases the NHGe either degraded or gave no reaction.

KW - N-heterocyclic germylenes

KW - crystal structure

KW - X-ray

U2 - 10.1155/2019/9178371

DO - 10.1155/2019/9178371

M3 - Article

VL - 2019

JO - Heteroatom Chemistry

JF - Heteroatom Chemistry

SN - 1042-7163

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ER -