Synthesis of cis - and trans-diisothiocyanato-bis(NHC) complexes of nickel(II) and applications in the Kumada-Corriu reaction

Ramasamy Jothibasu; Kuo-Wei Huang; Hanvinh Huynh

doi:10.1021/om100241v

Synthesis of cis - and trans-diisothiocyanato-bis(NHC) complexes of nickel(II) and applications in the Kumada-Corriu reaction

Ramasamy Jothibasu, Kuo-Wei Huang, Hanvinh Huynh

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

37 Scopus citations

Abstract

Metathetical reaction of AgSCN with a series of trans-dihalido-bis(carbene) nickel(II) complexes in CH3CN readily afforded the novel diisothiocyanato-bis(carbene) complexes [Ni(NCS)2(NHC)2] (trans-2a, NHC = 1,3-diisopropylbenzimidazolin-2-ylidene; trans-2b, NHC = 1,3-diisobutylbenzimidazolin-2-ylidene; trans-2c, NHC = 1,3- dibenzylbenzimidazolin-2-ylidene; cis-2d, NHC = 1,3-di(2-propenyl) benzimidazolin-2-ylidene; cis-2e, NHC = 1-propyl-3-methylbenzimidazolin-2- ylidene) as greenish-yellow powders in moderate to good yields. While dihalido-bis(carbene) Ni(II) complexes exclusively form trans-complexes, a trans-cis isomerization occurs upon halido-isothiocyanato exchange with complexes bearing less bulky carbene ligands, i.e., cis-2d/e. DFT calculations indicated that this isomerization can be attributed to a reduced energy difference between trans- and cis-isomers of diisothiocyanato complexes. All complexes have been characterized by multinuclear NMR spectroscopy, ESI mass spectrometry, and X-ray diffraction analysis. A catalytic study revealed that cis-complexes generally exhibit greater activities in the Kumada-Corriu coupling reaction. © 2010 American Chemical Society.

Original language	English (US)
Pages (from-to)	3746-3752
Number of pages	7
Journal	Organometallics
Volume	29
Issue number	17
DOIs	https://doi.org/10.1021/om100241v
State	Published - Sep 13 2010

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: Financial support from National University of Singapore (WBS R-143-000-327-133) to H.V.H and KAUST baseline funding to K.-W.H. is acknowledged. Technical support from staff at the CMMAC of the NUS Chemistry Department is appreciated. R.J. thanks NUS for a research scholarship.

ASJC Scopus subject areas

Organic Chemistry
Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/om100241v

Cite this

@article{87b6fc4119b94b099ed60614e6abf095,

title = "Synthesis of cis - and trans-diisothiocyanato-bis(NHC) complexes of nickel(II) and applications in the Kumada-Corriu reaction",

abstract = "Metathetical reaction of AgSCN with a series of trans-dihalido-bis(carbene) nickel(II) complexes in CH3CN readily afforded the novel diisothiocyanato-bis(carbene) complexes [Ni(NCS)2(NHC)2] (trans-2a, NHC = 1,3-diisopropylbenzimidazolin-2-ylidene; trans-2b, NHC = 1,3-diisobutylbenzimidazolin-2-ylidene; trans-2c, NHC = 1,3- dibenzylbenzimidazolin-2-ylidene; cis-2d, NHC = 1,3-di(2-propenyl) benzimidazolin-2-ylidene; cis-2e, NHC = 1-propyl-3-methylbenzimidazolin-2- ylidene) as greenish-yellow powders in moderate to good yields. While dihalido-bis(carbene) Ni(II) complexes exclusively form trans-complexes, a trans-cis isomerization occurs upon halido-isothiocyanato exchange with complexes bearing less bulky carbene ligands, i.e., cis-2d/e. DFT calculations indicated that this isomerization can be attributed to a reduced energy difference between trans- and cis-isomers of diisothiocyanato complexes. All complexes have been characterized by multinuclear NMR spectroscopy, ESI mass spectrometry, and X-ray diffraction analysis. A catalytic study revealed that cis-complexes generally exhibit greater activities in the Kumada-Corriu coupling reaction. {\textcopyright} 2010 American Chemical Society.",

author = "Ramasamy Jothibasu and Kuo-Wei Huang and Hanvinh Huynh",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: Financial support from National University of Singapore (WBS R-143-000-327-133) to H.V.H and KAUST baseline funding to K.-W.H. is acknowledged. Technical support from staff at the CMMAC of the NUS Chemistry Department is appreciated. R.J. thanks NUS for a research scholarship.",

year = "2010",

month = sep,

day = "13",

doi = "10.1021/om100241v",

language = "English (US)",

volume = "29",

pages = "3746--3752",

journal = "Organometallics",

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T1 - Synthesis of cis - and trans-diisothiocyanato-bis(NHC) complexes of nickel(II) and applications in the Kumada-Corriu reaction

AU - Jothibasu, Ramasamy

AU - Huang, Kuo-Wei

AU - Huynh, Hanvinh

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: Financial support from National University of Singapore (WBS R-143-000-327-133) to H.V.H and KAUST baseline funding to K.-W.H. is acknowledged. Technical support from staff at the CMMAC of the NUS Chemistry Department is appreciated. R.J. thanks NUS for a research scholarship.

PY - 2010/9/13

Y1 - 2010/9/13

N2 - Metathetical reaction of AgSCN with a series of trans-dihalido-bis(carbene) nickel(II) complexes in CH3CN readily afforded the novel diisothiocyanato-bis(carbene) complexes [Ni(NCS)2(NHC)2] (trans-2a, NHC = 1,3-diisopropylbenzimidazolin-2-ylidene; trans-2b, NHC = 1,3-diisobutylbenzimidazolin-2-ylidene; trans-2c, NHC = 1,3- dibenzylbenzimidazolin-2-ylidene; cis-2d, NHC = 1,3-di(2-propenyl) benzimidazolin-2-ylidene; cis-2e, NHC = 1-propyl-3-methylbenzimidazolin-2- ylidene) as greenish-yellow powders in moderate to good yields. While dihalido-bis(carbene) Ni(II) complexes exclusively form trans-complexes, a trans-cis isomerization occurs upon halido-isothiocyanato exchange with complexes bearing less bulky carbene ligands, i.e., cis-2d/e. DFT calculations indicated that this isomerization can be attributed to a reduced energy difference between trans- and cis-isomers of diisothiocyanato complexes. All complexes have been characterized by multinuclear NMR spectroscopy, ESI mass spectrometry, and X-ray diffraction analysis. A catalytic study revealed that cis-complexes generally exhibit greater activities in the Kumada-Corriu coupling reaction. © 2010 American Chemical Society.

AB - Metathetical reaction of AgSCN with a series of trans-dihalido-bis(carbene) nickel(II) complexes in CH3CN readily afforded the novel diisothiocyanato-bis(carbene) complexes [Ni(NCS)2(NHC)2] (trans-2a, NHC = 1,3-diisopropylbenzimidazolin-2-ylidene; trans-2b, NHC = 1,3-diisobutylbenzimidazolin-2-ylidene; trans-2c, NHC = 1,3- dibenzylbenzimidazolin-2-ylidene; cis-2d, NHC = 1,3-di(2-propenyl) benzimidazolin-2-ylidene; cis-2e, NHC = 1-propyl-3-methylbenzimidazolin-2- ylidene) as greenish-yellow powders in moderate to good yields. While dihalido-bis(carbene) Ni(II) complexes exclusively form trans-complexes, a trans-cis isomerization occurs upon halido-isothiocyanato exchange with complexes bearing less bulky carbene ligands, i.e., cis-2d/e. DFT calculations indicated that this isomerization can be attributed to a reduced energy difference between trans- and cis-isomers of diisothiocyanato complexes. All complexes have been characterized by multinuclear NMR spectroscopy, ESI mass spectrometry, and X-ray diffraction analysis. A catalytic study revealed that cis-complexes generally exhibit greater activities in the Kumada-Corriu coupling reaction. © 2010 American Chemical Society.

UR - http://hdl.handle.net/10754/561521

UR - https://pubs.acs.org/doi/abs/10.1021/om100241v

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U2 - 10.1021/om100241v

DO - 10.1021/om100241v

M3 - Article

SN - 0276-7333

VL - 29

SP - 3746

EP - 3752

JO - Organometallics

JF - Organometallics

IS - 17

ER -

Synthesis of cis - and trans-diisothiocyanato-bis(NHC) complexes of nickel(II) and applications in the Kumada-Corriu reaction

Abstract

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CCDC 813380: Experimental Crystal Structure Determination : trans-bis(1,3-Dibenzyl-2,3-dihydro-1H-benzimidazol-2-ylidene)-bis(thiocyanato)-nickel(ii)

CCDC 813382: Experimental Crystal Structure Determination : cis-bis(1-Methyl-3-propyl-2,3-dihydro-1H-benzimidazol-2-ylidene)-bis(thiocyanato)-nickel(ii)

CCDC 813379: Experimental Crystal Structure Determination : trans-bis(1,3-Di-isobutyl-2,3-dihydro-1H-benzimidazol-2-ylidene)-bis(thiocyanato)-nickel(ii)

Cite this

Synthesis of cis - and trans-diisothiocyanato-bis(NHC) complexes of nickel(II) and applications in the Kumada-Corriu reaction

Abstract

Bibliographical note

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 813380: Experimental Crystal Structure Determination : trans-bis(1,3-Dibenzyl-2,3-dihydro-1H-benzimidazol-2-ylidene)-bis(thiocyanato)-nickel(ii)

CCDC 813382: Experimental Crystal Structure Determination : cis-bis(1-Methyl-3-propyl-2,3-dihydro-1H-benzimidazol-2-ylidene)-bis(thiocyanato)-nickel(ii)

CCDC 813379: Experimental Crystal Structure Determination : trans-bis(1,3-Di-isobutyl-2,3-dihydro-1H-benzimidazol-2-ylidene)-bis(thiocyanato)-nickel(ii)

Cite this