Humboldt-Universität zu Berlin, Department of Chemistry, Brook-Taylor-Straße 2, D-12489 Berlin, Germany.
Dalton Trans. 2018 Nov 22;47(45):16299-16304. doi: 10.1039/c8dt03853h.
The peroxido complexes trans-[M(4-C5F4N)(O2)(CNtBu)(PR3)2] (1: M = Rh, R = Et; 2a: M = Ir, R = iPr) can be used in the metal-mediated hydrogenation of O2. The reaction of trans-[Rh(4-C5F4N)(O2)(CNtBu)(PEt3)2] (1) with B(C6F5)3 and H2 gave trans-[Rh(4-C5F4N)(CNtBu)(PEt3)2] (3), OPEt3 and (H2O)·B(C6F5)3, whereas treatment of [H(OEt2)2][B{3,5-(CF3)2C6H3}4] with 1 in the presence of H2 yielded trans-[Rh(4-C5F4N)(CNtBu)(PEt3)2] (3) and H2O2. The reactivity of 2a towards B(C6F5)3 and BClCy2 was also studied and an intermediate was detected which is assigned to be trans-[Ir(4-C5F4N)(Cl)(OOBCy2)(CNtBu)(PiPr3)2] (4a).
过氧配合物反式-[M(4-C5F4N)(O2)(CNtBu)(PR3)2]（1：M = Rh，R = Et；2a：M = Ir，R = iPr）可用于介导 O2 的加氢反应。反式-[Rh(4-C5F4N)(O2)(CNtBu)(PEt3)2]（1）与 B(C6F5)3 和 H2 的反应生成反式-[Rh(4-C5F4N)(CNtBu)(PEt3)2]（3）、OPEt3 和（H2O）·B(C6F5)3，而[H(OEt2)2][B{3,5-(CF3)2C6H3}4]与 1 在 H2 存在下的反应生成反式-[Rh(4-C5F4N)(CNtBu)(PEt3)2]（3）和 H2O2。还研究了 2a 对 B(C6F5)3 和 BClCy2 的反应性，并检测到一种中间体，其被分配为反式-[Ir(4-C5F4N)(Cl)(OOBCy2)(CNtBu)(PiPr3)2]（4a）。
