Facile and Room-Temperature Activation of C-sp3-Cl Bonds by Cheap and Air-Stable Nickel(II) Complexes of (N-Thioether) DPPA-Type Ligands

作者：Ghisolfi Alessio; Condello Francesca; Fliedel Christophe^*; Rosa Vitor; Braunstein Pierre

来源：Organometallics, 2015, 34(11): 2255-2260.

DOI：10.1021/om501004d

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)Ph-2}(n-PrSMe)-P,C)(2)] [BF4] (5) and [Ni((Ph2P)N{P(CH2)Ph-2}(p-(SMe)C6H4)-P,C)(2)][BF4](2) (6), respectively. The formation of [Ni((Ph2P)N{P(CH2)Ph-2}(nPrSMe)-P,C)(2)]Cl-2 (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.

• 出版日期2015-6-8