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 language | English |
|---|---|
| Pages (from-to) | 7661-7670 |
| Number of pages | 10 |
| Journal | Inorganic Chemistry |
| Volume | 44 |
| Issue number | 21 |
| DOIs | |
| Publication status | Published - Oct 17 2005 |
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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 journal › Article
}
TY - JOUR
T1 - General synthesis of Di-μ-oxo dimanganese complexes as functional models for the oxygen evolving complex of photosystem II
AU - Chen, Hongyu
AU - Tagore, Ranitendranath
AU - Das, Siddhartha
AU - Incarvito, Christopher
AU - Faller, J. W.
AU - Crabtree, Robert H.
AU - Brudvig, Gary W
PY - 2005/10/17
Y1 - 2005/10/17
N2 - 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.
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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U2 - 10.1021/ic0509940
DO - 10.1021/ic0509940
M3 - Article
C2 - 16212393
AN - SCOPUS:27544431556
VL - 44
SP - 7661
EP - 7670
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 21
ER -