A pentadentate nitrogen-rich copper electrocatalyst for water reduction with pH-dependent molecular mechanisms

Abstract

A copper catalyst is active towards water reduction with distinctive pH-dependent mechanisms. The CuIII–H− intermediate is bypassed by PCET processes.

Reactivity and Mechanisms of Photoactivated Heterometallic [RuIINiII] and [RuIINiIIRuII] Catalysts for Dihydrogen Generation from Water

“…However, this step requires 28 kcal mol À1 and is too costly. This observation aligns well with our previous results [17][18][19] in which the trivalent state is precluded in nickel and copper catalysts with p-acceptor ligands like pyridine and oxime, and renders 1C as catalytically inactive towards water reduction.…”

“…Our groups are engaged in the development of watersplitting catalysts containing abundant metals such as cobalt, [15,16] nickel and copper. [17,18] We recently developed an efficient Ni photocatalyst for water reduction, [19] as well as new oxime platforms, [20,21] and in the process we envisioned an oxime-based nickel catalyst covalently attached to a ruthenium photosensitizer. We hypothesize that this resulting heterometallic [(bpy) 2 Ru II Ni II (oxime)] species will enable electron transfer from the excited 4d 6 In this paper, we describe the concerted synthetic, electro/ photocatalytic, and computational effort to develop and probe heterometallic catalysts capable of photochemical production of hydrogen from water; the results follow.…”

Electro- and Solar-Driven Fuel Synthesis with First Row Transition Metal Complexes

“…Postelectrolysis SEM and X-ray photoelectron spectroscopy (XPS) analysis showed no evidence of electrodeposition, suggesting that the HEC is molecular in nature despite structural similarity to Cu1 . 332…”

Activation of ammonia and hydrazine by electron rich Fe(ii) complexes supported by a dianionic pentadentate ligand platform through a common terminal Fe(iii) amido intermediate

“…[9][10][11] These and related tetrapodal pentadentate platforms have been employed across the periodic table and have been successful at supporting a variety of metal centers in various oxidation states, mainly in the context of water oxidation/reduction catalysis. [29][30][31][32][33] Bullock and coworkers recently reported a detailed theoretical investigation using the PY5 ligand platform 34,35 for AO with M = Cr, Mo, W, Mn, Fe, Ru, Os. 36 They observed that the [PY5]Fe(II) complex behaved quite differently to the rest of the metals Please do not adjust margins Please do not adjust margins investigated, notably due to the significant radical character of the Fe-amido and Fe-imido intermediates computed.…”