Synthesis and Characterization of Oligonuclear Ru, Co and Cu Oxidation Catalysts

Abstract

In this work, we report the preparation and crystal structures of three new oligonuclear complexes, Ru2(bbpmp)(μ‐OAc)3 (4), [Co2(bbpmp)(μ‐OAc)(μ‐OMe)](PF6) (5), [Cu4(Hbbpmp)2(μ‐OAc)(H2O)2](OAc)(PF6)2 (6) {H3bbpmp = 2,6‐bis[(2‐hydroxybenzyl)‐(2‐pyridylmethyl)aminomethyl]‐4‐methyl‐phenol (3)}. The structures of the complexes were determined by single‐crystal X‐ray diffraction. The oxidation states of ruthenium, cobalt and copper in the complexes are +3, +3 and +2, respectively. In 4 and 5, RuIII and CoIII are coordinated to four oxygen and two nitrogen atoms in an octahedral geometry, while in 6, CuII adopts both octahedral (CuN2O4) and square‐pyramidal (CuN2O3) geometry. The potential of the three complexes as oxidation catalysts has been investigated.

Ruthenium Complexation in an Aluminium Metal–Organic Framework and Its Application in Alcohol Oxidation Catalysis

“…The method was expanded to other secondary alcohols by using the reaction conditions shown in Table 1, entry 5 and Table 2, entry 1. Benzylic sec ‐alcohols45 containing aromatic rings bearing electron‐donating and electron‐accepting groups were also oxidised to the corresponding ketones with nearly full conversion after 2–3 h (Table 2, entries 2–5). A variety of aliphatic cyclic and acyclic sec ‐alcohols were oxidised in excellent yield within 2–5 h (Table 2, entries 6–10).…”

Photosensitized Water Oxidation by Use of a Bioinspired Manganese Catalyst

“…We have therefore prepared complex 4, which is based on a new ligand, 3, that contains imidazole groups in place of the benzylic amines present in many previously reported manganese complexes (Scheme 1). [21,27,29] The ligand also contains negatively charged carboxylate groups, shown to dramatically reduce the redox potentials of the metal center, [14,15,28,29] which is required for use in a catalytic system with [Ru-(bpy) 3 ] 2+ -type photosensitizers. It is interesting to note that both imidazole and carboxylate groups act as ligands in the OEC.…”

Photosensitized Water Oxidation by Use of a Bioinspired Manganese Catalyst

“…We have therefore prepared complex 4 , which is based on a new ligand, 3 , that contains imidazole groups in place of the benzylic amines present in many previously reported manganese complexes (Scheme ) 21. 27, 29 The ligand also contains negatively charged carboxylate groups, shown to dramatically reduce the redox potentials of the metal center,14, 15, 28, 29 which is required for use in a catalytic system with [Ru(bpy) 3 ] 2+ ‐type photosensitizers. It is interesting to note that both imidazole and carboxylate groups act as ligands in the OEC 30.…”