Unexpected solvent-induced cis/trans isomerization and catalytic application of a bis-bidentate nickel(II) complex with N-heterocyclic carbene and amido functionalities

Chuang Yi Liao, Kai Ting Chan, Yu Chuan Chang, Chih Yuan Chen, Cheng Yi Tu, Ching-Han Hu, Hon Man Lee

Research output: Contribution to journalArticle

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Abstract

A series of bis-bidentate nickel(II) complexes with bifunctional ligands of N-heterocyclic carbene and amido moieties were prepared from the ligand precursors, [L1H1H2]Cl and [L2H 12H2]Cl (H1 = NHC=O, H2 = NCHN), in 48-82% yields. The complexes NiL21 and Ni(L2H1)2 are stable in the air and toward moisture. They are characterized by NMR (ID and 2D) and single-crystal X-ray diffraction studies. According to the NMR, crystallographic, and PXRD studies, one of the NiL21 complexes undergoes an intriguing reversible solvent-induced cis/trans transformation process, producing the eis form with DMSO and trans with CHCl3. The exchange process is highly specific and can be explained by the higher polarity of cis-NiL2 1, which favors the polar DMSO solvent, whereas the less polar trans form due to cancellation of polarity from the trans disposition of ligands favors the less polar CHCl3 solvent. A DFT calculation is in support of the experimental findings. Unlike the previous reported palladium analogues, NiL21 and Ni(L2H1)2, in the presence of PPh3 as cocatalyst, are highly efficient in catalyzing the Suzuki crosscoupling reaction of aryl chlorides with phenylboronic acid. A 3 mol % of NiL21 (Ni:PPh3 = 1:2) was sufficient to mediate the formation of 4-methoxy-1,1′-biphenyl from 4-chloroanisole in 95% yield in 12 h.

Original languageEnglish
Pages (from-to)5826-5833
Number of pages8
JournalOrganometallics
Volume26
Issue number24
DOIs
Publication statusPublished - 2007 Nov 19

Fingerprint

carbenes
Isomerization
Nickel
isomerization
nickel
Ligands
Dimethyl Sulfoxide
ligands
polarity
Nuclear magnetic resonance
nuclear magnetic resonance
Palladium
Discrete Fourier transforms
moisture
cancellation
Chlorides
palladium
Moisture
chlorides
Single crystals

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

@article{86334ee9faf249debf0b5d05d2128a92,
title = "Unexpected solvent-induced cis/trans isomerization and catalytic application of a bis-bidentate nickel(II) complex with N-heterocyclic carbene and amido functionalities",
abstract = "A series of bis-bidentate nickel(II) complexes with bifunctional ligands of N-heterocyclic carbene and amido moieties were prepared from the ligand precursors, [L1H1H2]Cl and [L2H 12H2]Cl (H1 = NHC=O, H2 = NCHN), in 48-82{\%} yields. The complexes NiL21 and Ni(L2H1)2 are stable in the air and toward moisture. They are characterized by NMR (ID and 2D) and single-crystal X-ray diffraction studies. According to the NMR, crystallographic, and PXRD studies, one of the NiL21 complexes undergoes an intriguing reversible solvent-induced cis/trans transformation process, producing the eis form with DMSO and trans with CHCl3. The exchange process is highly specific and can be explained by the higher polarity of cis-NiL2 1, which favors the polar DMSO solvent, whereas the less polar trans form due to cancellation of polarity from the trans disposition of ligands favors the less polar CHCl3 solvent. A DFT calculation is in support of the experimental findings. Unlike the previous reported palladium analogues, NiL21 and Ni(L2H1)2, in the presence of PPh3 as cocatalyst, are highly efficient in catalyzing the Suzuki crosscoupling reaction of aryl chlorides with phenylboronic acid. A 3 mol {\%} of NiL21 (Ni:PPh3 = 1:2) was sufficient to mediate the formation of 4-methoxy-1,1′-biphenyl from 4-chloroanisole in 95{\%} yield in 12 h.",
author = "Liao, {Chuang Yi} and Chan, {Kai Ting} and Chang, {Yu Chuan} and Chen, {Chih Yuan} and Tu, {Cheng Yi} and Ching-Han Hu and Lee, {Hon Man}",
year = "2007",
month = "11",
day = "19",
doi = "10.1021/om700607m",
language = "English",
volume = "26",
pages = "5826--5833",
journal = "Organometallics",
issn = "0276-7333",
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Unexpected solvent-induced cis/trans isomerization and catalytic application of a bis-bidentate nickel(II) complex with N-heterocyclic carbene and amido functionalities. / Liao, Chuang Yi; Chan, Kai Ting; Chang, Yu Chuan; Chen, Chih Yuan; Tu, Cheng Yi; Hu, Ching-Han; Lee, Hon Man.

In: Organometallics, Vol. 26, No. 24, 19.11.2007, p. 5826-5833.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Unexpected solvent-induced cis/trans isomerization and catalytic application of a bis-bidentate nickel(II) complex with N-heterocyclic carbene and amido functionalities

AU - Liao, Chuang Yi

AU - Chan, Kai Ting

AU - Chang, Yu Chuan

AU - Chen, Chih Yuan

AU - Tu, Cheng Yi

AU - Hu, Ching-Han

AU - Lee, Hon Man

PY - 2007/11/19

Y1 - 2007/11/19

N2 - A series of bis-bidentate nickel(II) complexes with bifunctional ligands of N-heterocyclic carbene and amido moieties were prepared from the ligand precursors, [L1H1H2]Cl and [L2H 12H2]Cl (H1 = NHC=O, H2 = NCHN), in 48-82% yields. The complexes NiL21 and Ni(L2H1)2 are stable in the air and toward moisture. They are characterized by NMR (ID and 2D) and single-crystal X-ray diffraction studies. According to the NMR, crystallographic, and PXRD studies, one of the NiL21 complexes undergoes an intriguing reversible solvent-induced cis/trans transformation process, producing the eis form with DMSO and trans with CHCl3. The exchange process is highly specific and can be explained by the higher polarity of cis-NiL2 1, which favors the polar DMSO solvent, whereas the less polar trans form due to cancellation of polarity from the trans disposition of ligands favors the less polar CHCl3 solvent. A DFT calculation is in support of the experimental findings. Unlike the previous reported palladium analogues, NiL21 and Ni(L2H1)2, in the presence of PPh3 as cocatalyst, are highly efficient in catalyzing the Suzuki crosscoupling reaction of aryl chlorides with phenylboronic acid. A 3 mol % of NiL21 (Ni:PPh3 = 1:2) was sufficient to mediate the formation of 4-methoxy-1,1′-biphenyl from 4-chloroanisole in 95% yield in 12 h.

AB - A series of bis-bidentate nickel(II) complexes with bifunctional ligands of N-heterocyclic carbene and amido moieties were prepared from the ligand precursors, [L1H1H2]Cl and [L2H 12H2]Cl (H1 = NHC=O, H2 = NCHN), in 48-82% yields. The complexes NiL21 and Ni(L2H1)2 are stable in the air and toward moisture. They are characterized by NMR (ID and 2D) and single-crystal X-ray diffraction studies. According to the NMR, crystallographic, and PXRD studies, one of the NiL21 complexes undergoes an intriguing reversible solvent-induced cis/trans transformation process, producing the eis form with DMSO and trans with CHCl3. The exchange process is highly specific and can be explained by the higher polarity of cis-NiL2 1, which favors the polar DMSO solvent, whereas the less polar trans form due to cancellation of polarity from the trans disposition of ligands favors the less polar CHCl3 solvent. A DFT calculation is in support of the experimental findings. Unlike the previous reported palladium analogues, NiL21 and Ni(L2H1)2, in the presence of PPh3 as cocatalyst, are highly efficient in catalyzing the Suzuki crosscoupling reaction of aryl chlorides with phenylboronic acid. A 3 mol % of NiL21 (Ni:PPh3 = 1:2) was sufficient to mediate the formation of 4-methoxy-1,1′-biphenyl from 4-chloroanisole in 95% yield in 12 h.

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