作者:Laurence R. Doyle、Ashley J. Wooles、Lucy C. Jenkins、Floriana Tuna、Eric J. L. McInnes、Stephen T. Liddle
DOI:10.1002/anie.201802576
日期:2018.5.22
Catalytic reduction of N2 to NH3 by a Ti complex has been achieved, thus now adding an early d‐block metal to the small group of mid‐ and late‐d‐block metals (Mo, Fe, Ru, Os, Co) that catalytically produce NH3 by N2 reduction and protonolysis under homogeneous, abiological conditions. Reduction of [TiIV(TrenTMS)X] (X=Cl, 1A; I, 1B; TrenTMS=N(CH2CH2NSiMe3)3) with KC8 affords [TiIII(TrenTMS)] (2). Addition
Ti络合物已将N 2催化还原为NH 3,因此现在将早期d嵌段金属添加到少量的中,后期d金属中(Mo,Fe,Ru,Os,Co)在均一的生物条件下,通过N 2还原和质子分解催化生成NH 3。用KC 8还原[Ti IV(Tren TMS)X](X = Cl,1A ; I,1B ; Tren TMS = N(CH 2 CH 2 NSiMe 3)3)得到[Ti III(Tren TMS)]](2)。N个加法2次,得到[(特伦TMS)的Ti III } 2(μ-η 1:η 1 -N 2)](3); 与KC进一步减少8给出[(特伦TMS)的Ti IV } 2(μ-η 1:η 1:η 2:η 2 -N 2 ķ 2)](4)。苯并-15-冠-5醚(B15C5)至加法4只得到[(特伦TMS)的Ti IV } 2(μ-η 1:η1- N 2)] [K(B15C5)2 ] 2(5)。配合物3 - 5氮气氛下处理2与KC