Dataset Information

A new decomposition mechanism for metal complexes under water-oxidation conditions.

ABSTRACT: Herein, water-oxidation reaction by cobalt(II) phthalocyanine, N,N'-bis (salicylidene) ethylenediamino cobalt(II), nickel(II) Schiff base (N,N'-bis (salicylidene)ethylenediamino nickel(II), nickel(II)) phthalocyanine-tetrasulfonate tetrasodium, manganese(II) phthalocyanine, 5,10,15,20-Tetraphenyl-21H,23H-porphine manganese(III) chloride, manganese(III) 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine chloride tetrakis(methochloride) was investigated using electrochemistry, UV-vis spectroscopy and spectroelectrochemistry. According to our results, a new decomposition pathway for these metal complexes under water-oxidation conditions was proposed. The produced metal oxide obtained by decomposition of metal complex under water -oxidation conditions not only catalyzes water-oxidation reaction but this metal oxide also accelerates decomposition of the corresponding complex to form higher amounts of the metal oxide. We hypothesize that such a mechanism could be investigated for many metal complexes under different oxidation or reduction reactions.

SUBMITTER: Najafpour MM

PROVIDER: S-EPMC6522543 | biostudies-literature | 2019 May

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

A new decomposition mechanism for metal complexes under water-oxidation conditions.

Najafpour Mohammad Mahdi MM Feizi Hadi H

Scientific reports 20190516 1

Herein, water-oxidation reaction by cobalt(II) phthalocyanine, N,N'-bis (salicylidene) ethylenediamino cobalt(II), nickel(II) Schiff base (N,N'-bis (salicylidene)ethylenediamino nickel(II), nickel(II)) phthalocyanine-tetrasulfonate tetrasodium, manganese(II) phthalocyanine, 5,10,15,20-Tetraphenyl-21H,23H-porphine manganese(III) chloride, manganese(III) 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine chloride tetrakis(methochloride) was investigated using electrochemistry, UV-vis spectroscopy and sp ...[more]

PMID: 31097740

Similar Datasets

Project description:A central question in biological water splitting concerns the oxidation states of the manganese ions that comprise the oxygen-evolving complex of photosystem II. Understanding the nature and order of oxidation events that occur during the catalytic cycle of five S i states (i = 0-4) is of fundamental importance both for the natural system and for artificial water oxidation catalysts. Despite the widespread adoption of the so-called "high-valent scheme"-where, for example, the Mn oxidation states in the S2 state are assigned as III, IV, IV, IV-the competing "low-valent scheme" that differs by a total of two metal unpaired electrons (i.e. III, III, III, IV in the S2 state) is favored by several recent studies for the biological catalyst. The question of the correct oxidation state assignment is addressed here by a detailed computational comparison of the two schemes using a common structural platform and theoretical approach. Models based on crystallographic constraints were constructed for all conceivable oxidation state assignments in the four (semi)stable S states of the oxygen evolving complex, sampling various protonation levels and patterns to ensure comprehensive coverage. The models are evaluated with respect to their geometric, energetic, electronic, and spectroscopic properties against available experimental EXAFS, XFEL-XRD, EPR, ENDOR and Mn K pre-edge XANES data. New 2.5 K 55Mn ENDOR data of the S2 state are also reported. Our results conclusively show that the entire S state phenomenology can only be accommodated within the high-valent scheme by adopting a single motif and protonation pattern that progresses smoothly from S0 (III, III, III, IV) to S3 (IV, IV, IV, IV), satisfying all experimental constraints and reproducing all observables. By contrast, it was impossible to construct a consistent cycle based on the low-valent scheme for all S states. Instead, the low-valent models developed here may provide new insight into the over-reduced S states and the states involved in the assembly of the catalytically active water oxidizing cluster.

Dataset Information

A new decomposition mechanism for metal complexes under water-oxidation conditions.

Publications

A new decomposition mechanism for metal complexes under water-oxidation conditions.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets