Department of Chemistry, Columbia University , 3000 Broadway, New York, New York 10027, United States.
J Am Chem Soc. 2017 Jun 14;139(23):7685-7688. doi: 10.1021/jacs.7b02183. Epub 2017 Jun 6.
Transfer of the first electron from (PhP)CuH to CpFe is fast (k > 10 L·mol·s). Transfer of a second electron to the same oxidant has a much lower thermodynamic driving force and is considerably slower, with k = 9.29(4) × 10 L·mol·s. The second oxidation leads to the formation of [(PhP)CuH]. The structure of [(PhP)CuH] has been confirmed by its conversion back to (PhP)CuH and by microanalysis; X-ray diffraction shows that the complex is a bitetrahedron in the solid state. [(PhP)CuH] can also be prepared by treating (PhP)CuH with MeOTf. With less than 1 equiv of CpFe as oxidant, (PhP)CuH gives [(PhP)CuH] as the major product; X-ray diffraction shows a Cu octahedron with one face capped by an additional Cu. [(PhP)CuH] can also be prepared by treating (PhP)CuH with [Cu(CHCN)] (along with 1 equiv of PhP), and can be converted back to (PhP)CuH with base/H.
（PhP）CuH 向 CpFe 的第一个电子转移很快（k > 10 L·mol·s）。向相同氧化剂转移第二个电子的热力学驱动力要低得多，速度也慢得多，k = 9.29(4) × 10 L·mol·s。第二次氧化导致[(PhP)CuH]的形成。[(PhP)CuH]的结构已通过其转化回（PhP）CuH 和微量分析得到证实；X 射线衍射表明该配合物在固态中为四面体。[(PhP)CuH]也可以通过用 MeOTf 处理（PhP）CuH 来制备。当氧化剂 CpFe 的用量少于 1 当量时，（PhP）CuH 主要生成[(PhP)CuH]；X 射线衍射显示一个具有一个额外 Cu 原子覆盖的 Cu 八面体。[(PhP)CuH]也可以通过用[Cu(CHCN)]（同时用 1 当量的 PhP）处理（PhP）CuH 来制备，并可以用碱/H 转化回（PhP）CuH。
