Dimer-of-dimers model for the oxygen-evolving complex of photosystem II. Synthesis and properties of MnIV4O5(terpy) 4(H2O)2](CIO4)6

Hongyu Chen; J. W. Faller; Robert H. Crabtree; Gary W. Brudvig

doi:10.1021/ja037389l

Dimer-of-dimers model for the oxygen-evolving complex of photosystem II. Synthesis and properties of Mn^IV₄O₅(terpy) ₄(H₂O)₂](CIO₄)₆

Hongyu Chen, J. W. Faller, Robert H. Crabtree, Gary W. Brudvig

Yale University

Research output: Contribution to journal › Article › peer-review

120 Citations (Scopus)

Abstract

A dimer-of-dimers model compound for the oxygen-evolving complex of photosystem II, [{(H₂O)-(terpy)Mn^IV(μ-O) ₂Mn^IV(terpy)}₂(μ-O)](CIO₄) ₆ (terpy = 2,2′:6′,2″-terpyridine), has been prepared and characterized by X-ray crystallography and ESI-MS. Low pH was found to promote the disproportionation of [Mn^III/IV ₂O₂(terpy)₂(OH₂)₂] ³⁺ to Mn²⁺ and a Mn^IV/IV₂O ₂(terpy)₂ species; the latter complex slowly dimerizes to form the title complex. Protonation of a μ-oxo bridge is proposed to initiate the disproportionation, based on analogy with the [Mn ^III/IV₂O₂(bpy)₄]³⁺ system.

Original language	English
Pages (from-to)	7345-7349
Number of pages	5
Journal	Journal of the American Chemical Society
Volume	126
Issue number	23
DOIs	https://doi.org/10.1021/ja037389l
Publication status	Published - Jun 16 2004

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

Access to Document

10.1021/ja037389l

Fingerprint Dive into the research topics of 'Dimer-of-dimers model for the oxygen-evolving complex of photosystem II. Synthesis and properties of MnIV4O5(terpy) 4(H2O)2](CIO4)6'. Together they form a unique fingerprint.

Cite this

@article{ef1d08d76e3747809593e3322fab1153,

title = "Dimer-of-dimers model for the oxygen-evolving complex of photosystem II. Synthesis and properties of MnIV4O5(terpy) 4(H2O)2](CIO4)6",

abstract = "A dimer-of-dimers model compound for the oxygen-evolving complex of photosystem II, [{(H2O)-(terpy)MnIV(μ-O) 2MnIV(terpy)}2(μ-O)](CIO4) 6 (terpy = 2,2′:6′,2″-terpyridine), has been prepared and characterized by X-ray crystallography and ESI-MS. Low pH was found to promote the disproportionation of [MnIII/IV 2O2(terpy)2(OH2)2] 3+ to Mn2+ and a MnIV/IV2O 2(terpy)2 species; the latter complex slowly dimerizes to form the title complex. Protonation of a μ-oxo bridge is proposed to initiate the disproportionation, based on analogy with the [Mn III/IV2O2(bpy)4]3+ system.",

author = "Hongyu Chen and Faller, {J. W.} and Crabtree, {Robert H.} and Brudvig, {Gary W.}",

year = "2004",

month = jun,

day = "16",

doi = "10.1021/ja037389l",

language = "English",

volume = "126",

pages = "7345--7349",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "23",

}

TY - JOUR

T1 - Dimer-of-dimers model for the oxygen-evolving complex of photosystem II. Synthesis and properties of MnIV4O5(terpy) 4(H2O)2](CIO4)6

AU - Chen, Hongyu

AU - Faller, J. W.

AU - Crabtree, Robert H.

AU - Brudvig, Gary W.

PY - 2004/6/16

Y1 - 2004/6/16

N2 - A dimer-of-dimers model compound for the oxygen-evolving complex of photosystem II, [{(H2O)-(terpy)MnIV(μ-O) 2MnIV(terpy)}2(μ-O)](CIO4) 6 (terpy = 2,2′:6′,2″-terpyridine), has been prepared and characterized by X-ray crystallography and ESI-MS. Low pH was found to promote the disproportionation of [MnIII/IV 2O2(terpy)2(OH2)2] 3+ to Mn2+ and a MnIV/IV2O 2(terpy)2 species; the latter complex slowly dimerizes to form the title complex. Protonation of a μ-oxo bridge is proposed to initiate the disproportionation, based on analogy with the [Mn III/IV2O2(bpy)4]3+ system.

AB - A dimer-of-dimers model compound for the oxygen-evolving complex of photosystem II, [{(H2O)-(terpy)MnIV(μ-O) 2MnIV(terpy)}2(μ-O)](CIO4) 6 (terpy = 2,2′:6′,2″-terpyridine), has been prepared and characterized by X-ray crystallography and ESI-MS. Low pH was found to promote the disproportionation of [MnIII/IV 2O2(terpy)2(OH2)2] 3+ to Mn2+ and a MnIV/IV2O 2(terpy)2 species; the latter complex slowly dimerizes to form the title complex. Protonation of a μ-oxo bridge is proposed to initiate the disproportionation, based on analogy with the [Mn III/IV2O2(bpy)4]3+ system.

UR - http://www.scopus.com/inward/record.url?scp=2942528725&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=2942528725&partnerID=8YFLogxK

U2 - 10.1021/ja037389l

DO - 10.1021/ja037389l

M3 - Article

C2 - 15186173

AN - SCOPUS:2942528725

VL - 126

SP - 7345

EP - 7349

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 23