Clapson Marissa L, Nelson David J, Drover Marcus W
Department of Chemistry and Biochemistry, The University of Windsor, 401 Sunset Avenue, Windsor, ON N9B 3P4, Canada.
WestCHEM Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, Scotland, U.K.
ACS Org Inorg Au. 2023 May 11;3(4):217-222. doi: 10.1021/acsorginorgau.3c00010. eCollection 2023 Aug 2.
Monodentate phosphine-ligated nickel compounds, , [Ni(PPh)] are relevant as active catalysts across a broad range of reactions. This report expands upon the coordination chemistry of this family, offering the reactivity of allyl- and vinyl-substituted diphenylphosphine (PPhR) with [Ni(COD)] (COD = 1,5-cyclooctadiene). These reactions provide three-coordinate dinickelacycles that are intermolecularly tethered through adjacent {Ni}-olefin interactions. The ring conformation of such cycles has been studied in the solid-state and using theoretical calculations. Here, a difference in reaction outcome is linked to the presence of an allyl vs vinyl group, where the former is observed to undergo rearrangement, bringing about challenges in clean product isolation.
单齿膦配位的镍化合物，如[Ni(PPh)]，在广泛的反应中作为活性催化剂具有重要意义。本报告扩展了该家族的配位化学，展示了烯丙基和乙烯基取代的二苯基膦（PPhR）与[Ni(COD)]（COD = 1,5 - 环辛二烯）的反应活性。这些反应生成了通过相邻的{Ni}-烯烃相互作用进行分子间连接的三配位双镍环。此类环的环构象已通过固态研究和理论计算进行了探究。在此，反应结果的差异与烯丙基和乙烯基的存在有关，其中观察到前者会发生重排，给纯净产物的分离带来了挑战。
