Trapping an elusive intermediate in manganese-oxo cubane chemistry

Jian Zhong Wu; Eric Sellitto; Glenn P.A. Yap; John Sheats; G. Charles Dismukes

doi:10.1021/ic048988b

Trapping an elusive intermediate in manganese-oxo cubane chemistry

Jian Zhong Wu, Eric Sellitto, Glenn P.A. Yap, John Sheats, G. Charles Dismukes

Rutgers University

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

53 Citations (Scopus)

Abstract

A new member of the Mn-oxo cubane core complex family [Mn ^2III,2IV₄O₄L₆] (1), where L = (p-MeOPh)₂PO₂^-, has been synthesized and characterized. Compound 1 possesses structurally inequivalent Mn^III and Mn^IV with clear valence electron localization in the crystal phase, quite unlike the structurally equivalent sites, tetrahedral core symmetry, and delocalized valence of its analogue where L = Ph ₂PO₂^-. Compound 1 exhibits appreciable positive shifts (0.1-0.3 V) of both the oxidation and reduction electrochemical potentials, attributable to the remote electron donating p-MeO groups. Reduction of 1 by methanol yields a novel core complex [Mn^III ₄O₂(OMe)₂(MeOH){(p-MeOPh)₂PO ₂}₆] (2). Each Mn^III of 2 is tetragonally distorted due to the Jahn-Teller effect with elongated Mn-O bonds that are directed at the two μ₃-MeO bridges and neither of the two μ₃-oxos. These electronically driven distortions provide a structural rationale for the greater basicity of the former sites and explain why 2 of the 4 corner oxos are preferentially reduced to water molecules.

Original language	English
Pages (from-to)	5795-5797
Number of pages	3
Journal	Inorganic Chemistry
Volume	43
Issue number	19
DOIs	https://doi.org/10.1021/ic048988b
Publication status	Published - Sep 20 2004

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Trapping an elusive intermediate in manganese-oxo cubane chemistry",

abstract = "A new member of the Mn-oxo cubane core complex family [Mn 2III,2IV4O4L6] (1), where L = (p-MeOPh)2PO2-, has been synthesized and characterized. Compound 1 possesses structurally inequivalent MnIII and MnIV with clear valence electron localization in the crystal phase, quite unlike the structurally equivalent sites, tetrahedral core symmetry, and delocalized valence of its analogue where L = Ph 2PO2-. Compound 1 exhibits appreciable positive shifts (0.1-0.3 V) of both the oxidation and reduction electrochemical potentials, attributable to the remote electron donating p-MeO groups. Reduction of 1 by methanol yields a novel core complex [MnIII 4O2(OMe)2(MeOH){(p-MeOPh)2PO 2}6] (2). Each MnIII of 2 is tetragonally distorted due to the Jahn-Teller effect with elongated Mn-O bonds that are directed at the two μ3-MeO bridges and neither of the two μ3-oxos. These electronically driven distortions provide a structural rationale for the greater basicity of the former sites and explain why 2 of the 4 corner oxos are preferentially reduced to water molecules.",

author = "Wu, {Jian Zhong} and Eric Sellitto and Yap, {Glenn P.A.} and John Sheats and Dismukes, {G. Charles}",

year = "2004",

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AU - Wu, Jian Zhong

AU - Sellitto, Eric

AU - Yap, Glenn P.A.

AU - Sheats, John

AU - Dismukes, G. Charles

PY - 2004/9/20

Y1 - 2004/9/20

N2 - A new member of the Mn-oxo cubane core complex family [Mn 2III,2IV4O4L6] (1), where L = (p-MeOPh)2PO2-, has been synthesized and characterized. Compound 1 possesses structurally inequivalent MnIII and MnIV with clear valence electron localization in the crystal phase, quite unlike the structurally equivalent sites, tetrahedral core symmetry, and delocalized valence of its analogue where L = Ph 2PO2-. Compound 1 exhibits appreciable positive shifts (0.1-0.3 V) of both the oxidation and reduction electrochemical potentials, attributable to the remote electron donating p-MeO groups. Reduction of 1 by methanol yields a novel core complex [MnIII 4O2(OMe)2(MeOH){(p-MeOPh)2PO 2}6] (2). Each MnIII of 2 is tetragonally distorted due to the Jahn-Teller effect with elongated Mn-O bonds that are directed at the two μ3-MeO bridges and neither of the two μ3-oxos. These electronically driven distortions provide a structural rationale for the greater basicity of the former sites and explain why 2 of the 4 corner oxos are preferentially reduced to water molecules.

AB - A new member of the Mn-oxo cubane core complex family [Mn 2III,2IV4O4L6] (1), where L = (p-MeOPh)2PO2-, has been synthesized and characterized. Compound 1 possesses structurally inequivalent MnIII and MnIV with clear valence electron localization in the crystal phase, quite unlike the structurally equivalent sites, tetrahedral core symmetry, and delocalized valence of its analogue where L = Ph 2PO2-. Compound 1 exhibits appreciable positive shifts (0.1-0.3 V) of both the oxidation and reduction electrochemical potentials, attributable to the remote electron donating p-MeO groups. Reduction of 1 by methanol yields a novel core complex [MnIII 4O2(OMe)2(MeOH){(p-MeOPh)2PO 2}6] (2). Each MnIII of 2 is tetragonally distorted due to the Jahn-Teller effect with elongated Mn-O bonds that are directed at the two μ3-MeO bridges and neither of the two μ3-oxos. These electronically driven distortions provide a structural rationale for the greater basicity of the former sites and explain why 2 of the 4 corner oxos are preferentially reduced to water molecules.

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Trapping an elusive intermediate in manganese-oxo cubane chemistry

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