Facile and Room-Temperature Activation of Csp3-Cl Bonds by Cheap and Air-Stable Nickel(II) Complexes of (N-Thioether) DPPA-Type Ligands

Alessio Ghisolfi; Francesca Condello; Christophe Fliedel; Vitor Rosa; Pierre Braunstein

doi:10.1021/om501004d

Facile and Room-Temperature Activation of C_sp3-Cl Bonds by Cheap and Air-Stable Nickel(II) Complexes of (N-Thioether) DPPA-Type Ligands

Alessio Ghisolfi, Francesca Condello, Christophe Fliedel, Vitor Rosa, Pierre Braunstein

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

16 Citations (Scopus)

Abstract

Reaction of the diphosphine (P,P) ligand N(PPh₂)₂(n-PrSMe) (1) or N(PPh₂)₂(p-(SMe)C₆H₄) (2) with [Ni(NCMe)₆][BF₄]₂ in a 2:1 molar ratio afforded the bis-chelated, dicationic Ni(II) complexes [Ni(1)₂][BF₄]₂ (3) and [Ni(2)₂][BF₄]₂ (4), respectively. Both complexes were characterized in solution by various spectroscopic techniques and in the solid state by X-ray diffraction studies. In the presence of Zn metal used as cheap reductant, complexes 3 and 4 activate the inert C-Cl bonds of dichloromethane at room temperature to afford in high yield the phosphonium ylide derivatives [Ni((Ph₂P)N{P(CH₂)Ph₂}(n-PrSMe)-P,C)₂][BF₄]₂ (5) and [Ni((Ph₂P)N{P(CH₂)Ph₂}(p-(SMe)C₆H₄)-P,C)₂][BF₄]₂ (6), respectively. The formation of [Ni((Ph₂P)N{P(CH₂)Ph₂}(n-PrSMe)-P,C)₂]Cl₂ (5′), an analogue of complex 5, from a Ni(0) precursor supports the reduction of the Ni(II) precursors by the Zn reagent prior to C-Cl bond activation. The structures of 5 and 5′ were unambiguously established by X-ray diffraction analysis. (Chemical Equation Presented).

Original language	English
Pages (from-to)	2255-2260
Number of pages	6
Journal	Organometallics
Volume	34
Issue number	11
DOIs	https://doi.org/10.1021/om501004d
Publication status	Published - 8 Jun 2015

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@article{5a72177b71a54738808b625db145b16f,

title = "Facile and Room-Temperature Activation of Csp3-Cl Bonds by Cheap and Air-Stable Nickel(II) Complexes of (N-Thioether) DPPA-Type Ligands",

abstract = "Reaction of the diphosphine (P,P) ligand N(PPh2)2(n-PrSMe) (1) or N(PPh2)2(p-(SMe)C6H4) (2) with [Ni(NCMe)6][BF4]2 in a 2:1 molar ratio afforded the bis-chelated, dicationic Ni(II) complexes [Ni(1)2][BF4]2 (3) and [Ni(2)2][BF4]2 (4), respectively. Both complexes were characterized in solution by various spectroscopic techniques and in the solid state by X-ray diffraction studies. In the presence of Zn metal used as cheap reductant, complexes 3 and 4 activate the inert C-Cl bonds of dichloromethane at room temperature to afford in high yield the phosphonium ylide derivatives [Ni((Ph2P)N{P(CH2)Ph2}(n-PrSMe)-P,C)2][BF4]2 (5) and [Ni((Ph2P)N{P(CH2)Ph2}(p-(SMe)C6H4)-P,C)2][BF4]2 (6), respectively. The formation of [Ni((Ph2P)N{P(CH2)Ph2}(n-PrSMe)-P,C)2]Cl2 (5′), an analogue of complex 5, from a Ni(0) precursor supports the reduction of the Ni(II) precursors by the Zn reagent prior to C-Cl bond activation. The structures of 5 and 5′ were unambiguously established by X-ray diffraction analysis. (Chemical Equation Presented).",

author = "Alessio Ghisolfi and Francesca Condello and Christophe Fliedel and Vitor Rosa and Pierre Braunstein",

note = "We are grateful to the CNRS, the Ministere de la Recherche (Paris), the DFH/UFA (International Research Training Group 532-GRK532, Ph.D. grants to C.F. and A.G.), and the Fundacao para a Ciencia e Tecnologia (FCT) (fellowships SFRH/BPD/73253/2010 to C.F. and SFRH/BPD/44262/2008 to V.R.) for funding.",

year = "2015",

month = jun,

day = "8",

doi = "10.1021/om501004d",

language = "English",

volume = "34",

pages = "2255--2260",

journal = "Organometallics",

issn = "0276-7333",

publisher = "ACS - American Chemical Society",

number = "11",

}

TY - JOUR

T1 - Facile and Room-Temperature Activation of Csp3-Cl Bonds by Cheap and Air-Stable Nickel(II) Complexes of (N-Thioether) DPPA-Type Ligands

AU - Ghisolfi, Alessio

AU - Condello, Francesca

AU - Fliedel, Christophe

AU - Rosa, Vitor

AU - Braunstein, Pierre

N1 - We are grateful to the CNRS, the Ministere de la Recherche (Paris), the DFH/UFA (International Research Training Group 532-GRK532, Ph.D. grants to C.F. and A.G.), and the Fundacao para a Ciencia e Tecnologia (FCT) (fellowships SFRH/BPD/73253/2010 to C.F. and SFRH/BPD/44262/2008 to V.R.) for funding.

PY - 2015/6/8

Y1 - 2015/6/8

N2 - Reaction of the diphosphine (P,P) ligand N(PPh2)2(n-PrSMe) (1) or N(PPh2)2(p-(SMe)C6H4) (2) with [Ni(NCMe)6][BF4]2 in a 2:1 molar ratio afforded the bis-chelated, dicationic Ni(II) complexes [Ni(1)2][BF4]2 (3) and [Ni(2)2][BF4]2 (4), respectively. Both complexes were characterized in solution by various spectroscopic techniques and in the solid state by X-ray diffraction studies. In the presence of Zn metal used as cheap reductant, complexes 3 and 4 activate the inert C-Cl bonds of dichloromethane at room temperature to afford in high yield the phosphonium ylide derivatives [Ni((Ph2P)N{P(CH2)Ph2}(n-PrSMe)-P,C)2][BF4]2 (5) and [Ni((Ph2P)N{P(CH2)Ph2}(p-(SMe)C6H4)-P,C)2][BF4]2 (6), respectively. The formation of [Ni((Ph2P)N{P(CH2)Ph2}(n-PrSMe)-P,C)2]Cl2 (5′), an analogue of complex 5, from a Ni(0) precursor supports the reduction of the Ni(II) precursors by the Zn reagent prior to C-Cl bond activation. The structures of 5 and 5′ were unambiguously established by X-ray diffraction analysis. (Chemical Equation Presented).

AB - Reaction of the diphosphine (P,P) ligand N(PPh2)2(n-PrSMe) (1) or N(PPh2)2(p-(SMe)C6H4) (2) with [Ni(NCMe)6][BF4]2 in a 2:1 molar ratio afforded the bis-chelated, dicationic Ni(II) complexes [Ni(1)2][BF4]2 (3) and [Ni(2)2][BF4]2 (4), respectively. Both complexes were characterized in solution by various spectroscopic techniques and in the solid state by X-ray diffraction studies. In the presence of Zn metal used as cheap reductant, complexes 3 and 4 activate the inert C-Cl bonds of dichloromethane at room temperature to afford in high yield the phosphonium ylide derivatives [Ni((Ph2P)N{P(CH2)Ph2}(n-PrSMe)-P,C)2][BF4]2 (5) and [Ni((Ph2P)N{P(CH2)Ph2}(p-(SMe)C6H4)-P,C)2][BF4]2 (6), respectively. The formation of [Ni((Ph2P)N{P(CH2)Ph2}(n-PrSMe)-P,C)2]Cl2 (5′), an analogue of complex 5, from a Ni(0) precursor supports the reduction of the Ni(II) precursors by the Zn reagent prior to C-Cl bond activation. The structures of 5 and 5′ were unambiguously established by X-ray diffraction analysis. (Chemical Equation Presented).

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U2 - 10.1021/om501004d

DO - 10.1021/om501004d

M3 - Article

AN - SCOPUS:84931291608

SN - 0276-7333

VL - 34

SP - 2255

EP - 2260

JO - Organometallics

JF - Organometallics

IS - 11

ER -

Facile and Room-Temperature Activation of C_sp3-Cl Bonds by Cheap and Air-Stable Nickel(II) Complexes of (N-Thioether) DPPA-Type Ligands

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