General synthesis of Di-μ-oxo dimanganese complexes as functional models for the oxygen evolving complex of photosystem II

Hongyu Chen, Ranitendranath Tagore, Siddhartha Das, Christopher Incarvito, J. W. Faller, Robert H. Crabtree, Gary W Brudvig

Research output: Contribution to journalArticle

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Abstract

A series of complexes with the formula [MnIII/IV 2(μ-O)2(L)2(X)2]3+ have been prepared in situ from MnIILCl2 precursors by a general preparative method (L = terpy, Cl-terpy, Br-terpy, Ph-terpy, tolyl-terpy, mesityl-terpy, tBu3-terpy, EtO-terpy, py-phen, dpya, Me2N-terpy, or HO-terpy, and X = a labile ligand such as water, chloride, or sulfate). The parent complex, where L = terpy and X = water, is a functional model for the oxygen-evolving complex of photosystem II (Limburg, et al. J. Am. Chem. Soc. 2001, 123, 423-430). Crystals of MnII(dpya) Cl2, MnII(Ph-terpy)-Cl2, Mn II(mesityl-terpy)Cl2, and an organic-soluble di-μ-oxo di-aqua dimanganese complex, [MnIII/IV2(μ-O) 2(mesityl-terpy)2(OH2)2](NO 3)3, were obtained and characterized by X-ray crystallography. Solutions of the in situ-formed di-μ-oxo dimanganese complexes were characterized by electrospray mass spectrometry, EPR spectroscopy, and UV-visible spectroscopy, and the rates of catalytic oxygen-evolving activity were assayed. The use of MnIILCl2 precursors leads to higher product purity of the Mn dimers while achieving the 1:1 ligand to Mn stoichiometry appropriate for catalytic activity assay. These methods can be used to screen the catalytic activity of other di-μ-oxo dimanganese complexes generated by using a ligand library.

Original languageEnglish
Pages (from-to)7661-7670
Number of pages10
JournalInorganic Chemistry
Volume44
Issue number21
DOIs
Publication statusPublished - Oct 17 2005

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Photosystem II Protein Complex
Oxygen
Ligands
ligands
catalytic activity
Catalyst activity
oxygen
synthesis
Spectroscopy
Water
X ray crystallography
Stoichiometry
Dimers
water
spectroscopy
Sulfates
crystallography
Mass spectrometry
Paramagnetic resonance
Chlorides

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

General synthesis of Di-μ-oxo dimanganese complexes as functional models for the oxygen evolving complex of photosystem II. / Chen, Hongyu; Tagore, Ranitendranath; Das, Siddhartha; Incarvito, Christopher; Faller, J. W.; Crabtree, Robert H.; Brudvig, Gary W.

In: Inorganic Chemistry, Vol. 44, No. 21, 17.10.2005, p. 7661-7670.

Research output: Contribution to journalArticle

Chen, Hongyu ; Tagore, Ranitendranath ; Das, Siddhartha ; Incarvito, Christopher ; Faller, J. W. ; Crabtree, Robert H. ; Brudvig, Gary W. / General synthesis of Di-μ-oxo dimanganese complexes as functional models for the oxygen evolving complex of photosystem II. In: Inorganic Chemistry. 2005 ; Vol. 44, No. 21. pp. 7661-7670.
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AB - A series of complexes with the formula [MnIII/IV 2(μ-O)2(L)2(X)2]3+ have been prepared in situ from MnIILCl2 precursors by a general preparative method (L = terpy, Cl-terpy, Br-terpy, Ph-terpy, tolyl-terpy, mesityl-terpy, tBu3-terpy, EtO-terpy, py-phen, dpya, Me2N-terpy, or HO-terpy, and X = a labile ligand such as water, chloride, or sulfate). The parent complex, where L = terpy and X = water, is a functional model for the oxygen-evolving complex of photosystem II (Limburg, et al. J. Am. Chem. Soc. 2001, 123, 423-430). Crystals of MnII(dpya) Cl2, MnII(Ph-terpy)-Cl2, Mn II(mesityl-terpy)Cl2, and an organic-soluble di-μ-oxo di-aqua dimanganese complex, [MnIII/IV2(μ-O) 2(mesityl-terpy)2(OH2)2](NO 3)3, were obtained and characterized by X-ray crystallography. Solutions of the in situ-formed di-μ-oxo dimanganese complexes were characterized by electrospray mass spectrometry, EPR spectroscopy, and UV-visible spectroscopy, and the rates of catalytic oxygen-evolving activity were assayed. The use of MnIILCl2 precursors leads to higher product purity of the Mn dimers while achieving the 1:1 ligand to Mn stoichiometry appropriate for catalytic activity assay. These methods can be used to screen the catalytic activity of other di-μ-oxo dimanganese complexes generated by using a ligand library.

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