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

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13 Citations (Scopus)


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 languageEnglish
Pages (from-to)2255-2260
Number of pages6
Issue number11
Publication statusPublished - 8 Jun 2015

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