Rapid water oxidation electrocatalysis by a ruthenium complex of the tripodal ligand tris(2-pyridyl)phosphine oxide

Abstract

A ruthenium complex of the tripodal ligand tris(2-pyridyl)phosphine oxide exhibits rapid water oxidation electrocatalysis over a wide pH range.

How Changing the Bridgehead Can Affect the Properties of Tripodal Ligands

“…[1][2][3][4][5][6] Preeminent in this area are tris-pyrazolyl borates (Figure 1a), which have found countless applications as ancillary ligands over the last three decades in catalytic and biomimetic systems. The primary influence on coordination behaviour is the increasing Lewis acidity (electropositivity) of the bridgehead atom as Group 15 is descended, whichn ot only modulates the electron density on the pyridyl donor groups but also introduces the potential for anion selective coordination behaviour.…”

“…[1][2][3][4][5][6] Preeminent in this area are tris-pyrazolyl borates (Figure 1a), which have found countless applications as ancillary ligands over the last three decades in catalytic and biomimetic systems. [1][2][3][4][5][6] Preeminent in this area are tris-pyrazolyl borates (Figure 1a), which have found countless applications as ancillary ligands over the last three decades in catalytic and biomimetic systems.…”

Homogeneous Electrocatalytic Water Oxidation by a Rigid Macrocyclic Copper(II) Complex

“…As shown in Figure 1, the Cu 2＋ center is penta-coordinated by four nitrogen atoms from the ligand and one water molecule, featuring a distorted trigonal bipyramidal geometry. The Cu -O distance of 2.1707 (16) Å is shorter than four Cu-N distances of 2.0455(17)-2.1707(18) Å. The redox properties of 1 were studied by cyclic voltammetry at a GC electrode (0.07 cm 2 ) in the presence of 1.0 mmol•L 1 1 in a 0.15 mmol•L 1 sodium phosphate (NaPi) buffer at pH 12.0.…”

“…In this context, water soluble, molecular WOCs are advantageous for controllable redox properties and mechanistic studies, and thus more amenable for further optimization. [14] Among them, high efficiency of WOCs based on Ru [13,15,16] and Ir [17,18] is impressive, while their further applications are limited by their prohibitive cost and scarcity. Thus, molecular WOCs featuring first-row transition metals, such as Mn, [19][20][21] Fe, [10,[22][23][24] Co, [25][26][27][28][29][30] Ni [11,31,32] and Cu [9,[33][34][35] have been broadly investigated.…”

Variable coordination of tris(2-pyridyl)phosphine and its oxide toward M(hfac)2: a metal-specifiable switching between the formation of mono- and bis-scorpionate complexes

“…29 Therefore, the further development of the coordination chemistry of tris(2-pyridyl)phosphine and its chalcogenides appears to be particularly appealing to access novel functional compounds. Herein, as a part of our ongoing interest in this area, we report on the variable coordination of tris(2-pyridyl) phosphine (1) and its oxide (2) towards M(hfac) 2 (M = Cu, Ni, Co, Mn) leading to either scorpionate or bis-scorpionate complexes.…”