镓-锌键间氢的溶剂依赖性氧化加成与还原消除反应
Solvent-Dependent Oxidative Addition and Reductive Elimination of H Across a Gallium-Zinc Bond.
作者信息
Morris Louis J, Rajeshkumar Thayalan, Okumura Akira, Maron Laurent, Okuda Jun
机构信息
Institute for Inorganic Chemistry, RWTH Aachen University, 52062, Aachen, Germany.
Chemistry Research Laboratory, University of Oxford, Oxford, OX1 3TA, UK.
出版信息
Angew Chem Int Ed Engl. 2022 Sep 5;61(36):e202208855. doi: 10.1002/anie.202208855. Epub 2022 Aug 4.
H adds reversibly across the metal-metal bond of [(BDI)Ga(H)-Zn(tmeda)(thf)][BAr ] (BDI=[HC{C(CH )N(2,6-iPr -C H )} ] , TMEDA=N,N,N',N'-tetramethylethylenediamine, BAr =[B(C H -3,5-(CF ) ) ] ). Due to the stabilising effect of solvent coordination, hydrogenation products [(BDI)GaH ] and [(tmeda)ZnH(thf)][BAr ] are favoured in THF solution, but THF-free mixtures of [(BDI)GaH ] and [(tmeda)ZnH(OEt )][BAr ] are predisposed towards entropically driven dehydrogenation to [(BDI)Ga(H)-Zn(tmeda)][BAr ] in fluorobenzene solution.
H可逆地加成到[(BDI)Ga(H)-Zn(tmeda)(thf)][BAr ]（BDI = [HC{C(CH )N(2,6-iPr -C H )} ] ，TMEDA = N,N,N',N'-四甲基乙二胺，BAr = [B(C H -3,5-(CF ) ) ] ）的金属-金属键上。由于溶剂配位的稳定作用，在四氢呋喃（THF）溶液中，氢化产物[(BDI)GaH ]和[(tmeda)ZnH(thf)][BAr ]更受青睐，但在氟苯溶液中，[(BDI)GaH ]和[(tmeda)ZnH(OEt )][BAr ]的无THF混合物倾向于熵驱动脱氢生成[(BDI)Ga(H)-Zn(tmeda)][BAr ] 。
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