Intervalence Transfer between Hexaaminecobalt(<scp>III</scp>) and Hexacyanoruthenate(<scp>II</scp>)

Vogler, Arnd; Kisslinger, Josef

doi:10.1002/anie.198200772

Cited by 2 publications

(1 citation statement)

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“…It is proposed that this band corresponds to a mixedmetal-ligand-to-ligand transition (MMLLT) with metal orbital participation, since the difference in the electronic structure of the ligands partially abates the delocalized bonding scheme usually observed for bis(1,2-dithiolene) complexes. In fact, for this compound it has been suggested that the mnt ligand is present in the dithiolate form due to the electron-accepting properties of the nitrile groups, while the other ligand is in the dithioketone form, [31] as reported for similar push-pull complexes [28] (Figure 1). Cyclic voltammetry in DMF showed a reversible reduction wave observed at -0.758 V vs. Fc +/0 , corresponding to the reduction of the complex to the dianion.…”

Section: Synthesis and Characterization Of Heteroleptic Dithiolene Comentioning

confidence: 59%

Establishing Structure–Activity Relationships in Photocatalytic Systems by Using Nickel Bis(dithiolene) Complexes as Proton Reduction Catalysts

et al. 2019

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Herein, we present an artificial photocatalytic system for H2 evolution based on a series of proton reduction catalysts, namely [Ni{S2C2(Ph)2}2] (1), [Ni{S2C2(Ph)2}2](NEt4) (1–), [Ni{S2C2(Ph)(Ph–OCH3‐4)}2] (2), [Ni{S2C2(Ph)(Ph–OCH3‐4)}2](NEt4) (2–), [Ni{S2C2(Ph–OCH3‐4)2}2] (3) and [Ni{S2C2(Ph–OCH3‐4)2}2](NEt4) (3–), [Ni(mnt)2] (NBu4) (4–), [Ni(mnt)(S2C2(Ph)2)](NBu4) (5–). These complexes are different of both in charge and the substituents on dithiolene ligand and represent a group of active catalysts for the reduction of protons with high TONs. A series of ReI complexes, [ReBr(CO)3 (bpy)], [ReCl(CO)3(bpy)], [Re(NCS)(CO3)(bpy)], [ReBr(CO)3(amphen)] and [ReBr(CO)3 (pq)] were used as photosensitizers, in combination with triethanolamine as a sacrificial electron donor and acetic acid as a proton source. The differences of the ligands in the electron donating properties and reactivity are discussed in the light of the experimental data. We also present the physicochemical characterization of a previously reported heteroleptic monoanionic complex (5–), by UV/Vis spectroscopy, FTIR spectroscopy, cyclic voltammetry and single‐crystal X‐ray diffraction studies.

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Section: Synthesis and Characterization Of Heteroleptic Dithiolene Comentioning

confidence: 59%