空间位阻镍-多吡啶配合物的还原消除反应

Day Craig S, Ton Stephanie J, McGuire Ryan T, Foroutan-Nejad Cina, Martin Ruben

The Barcelona Institute of Science and Technology, Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona, Spain.

Departament de Química Analítica i Química Orgànica, Universitat Rovira i Virgili, c/Marcel·lí Domingo 1, 43007 Tarragona, Spain.

Organometallics. 2022 Oct 10;41(19):2662-2667. doi: 10.1021/acs.organomet.2c00362. Epub 2022 Sep 21.

Herein we disclose the synthesis of sterically encumbered dialkylnickel(II) complexes bearing 2,9-dimethyl-1,10-phenanthroline ligands. A comparison with their unsubstituted analogues by both X-ray crystallography and theoretical calculations revealed significant distortions in their molecular structures. Eyring plots along with stoichiometric and photoexcitation studies revealed that sterically encumbered dialkylnickel(II) complexes enable facile C( )-C( ) reductive elimination, thus offering an improved understanding of Ni catalysis.

在此，我们披露了带有2,9 - 二甲基 - 1,10 - 菲咯啉配体的空间位阻二烷基镍（II）配合物的合成。通过X射线晶体学和理论计算将它们与其未取代的类似物进行比较，结果表明其分子结构存在显著扭曲。艾林曲线以及化学计量和光激发研究表明，空间位阻二烷基镍（II）配合物能够实现容易的C（）-C（）还原消除，从而有助于更好地理解镍催化作用。