Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701, Republic of Korea.
J Am Chem Soc. 2015 Apr 8;137(13):4280-3. doi: 10.1021/ja513112r. Epub 2015 Mar 26.
Reversible transformations are observed between a phosphide-nickel(II) alkoxide and a phosphinite-nickel(0) species via a P-O bond formation coupled with a 2-e(-) redox change at the nickel center. In the forward reaction, the nickel(0) dinitrogen species (PP(OMe)P)Ni(N2) (2) and {(PP(OMe)P)Ni}2(μ-N2) (3) were formed from the reaction of (PPP)NiCl (1) with a methoxy anion. In the backward reaction, a (PPP)Ni(II) moiety was regenerated from the CO2 reaction of 3 with the concomitant formation of a methyl carbonate ligand in (PPP)Ni(OCOOMe) (7). Thus, unanticipated metal-ligand cooperation involving a phosphide based ligand is reported.
通过镍中心的 P-O 键形成和 2e(-) 氧化还原变化，膦镍(II)烷氧基化合物和膦亚膦酸镍(0)物种之间观察到可逆转化。在正向反应中，镍(0)二氮物种(PP(OME)P)Ni(N2)(2)和{(PP(OME)P)Ni}2(μ-N2)(3)是由(PPP)NiCl(1)与甲氧基阴离子反应生成的。在逆向反应中，3 与 CO2 的反应生成(PPP)Ni(OCOOMe)(7)，同时形成甲基碳酸酯配体，从而使(PPP)Ni(II)部分再生。因此，报告了一种涉及基于膦的配体的意想不到的金属-配体协同作用。
