Department of Chemistry, 6-335, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139-4307, USA.
J Am Chem Soc. 2011 Jun 1;133(21):8114-7. doi: 10.1021/ja201972v. Epub 2011 May 9.
The two-electron mixed-valence dirhodium complex Rh(2)(0,II)(tfepma)(2)(CN(t)Bu)(2)Cl(2) (tfepma = CH(3)NP(OCH(2)CF(3))(2)) reacts with HCl to furnish two isomeric dirhodium hydrido-chloride complexes, Rh(2)(II,II)(tfepma)(2)(CN(t)Bu)(2)Cl(3)H. In the presence of HCl, the hydride complex effects the reduction of 0.5 equiv of O(2) to 1 equiv of H(2)O, generating Rh(2)(II,II)(tfepma)(2)(CN(t)Bu)(2)Cl(4), which can be prepared independently by chlorine oxidation of the Rh(2)(0,II) precursor. The starting Rh(2)(0,II) complex is regenerated photochemically to close an oxygen-to-water reduction photocycle.
二电子混合价态双铑配合物 Rh(2)(0,II)(tfepma)(2)(CN(t)Bu)(2)Cl(2) (tfepma = CH(3)NP(OCH(2)CF(3))(2)) 与 HCl 反应生成两种异构的双铑氢氯化物配合物，Rh(2)(II,II)(tfepma)(2)(CN(t)Bu)(2)Cl(3)H。在 HCl 的存在下，氢化物配合物将 0.5 当量的 O(2)还原为 1 当量的 H(2)O，生成 Rh(2)(II,II)(tfepma)(2)(CN(t)Bu)(2)Cl(4)，后者可通过对 Rh(2)(0,II)前体的氯气氧化来独立制备。通过光化学再生起始 Rh(2)(0,II)配合物，以封闭氧到水的还原光循环。
