Trapping an elusive intermediate in manganese-oxo cubane chemistry

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

Research output: Contribution to journalArticle

52 Citations (Scopus)

Abstract

A new member of the Mn-oxo cubane core complex family [Mn 2III,2IV 4O4L6] (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.

Original languageEnglish
Pages (from-to)5795-5797
Number of pages3
JournalInorganic Chemistry
Volume43
Issue number19
DOIs
Publication statusPublished - Sep 20 2004

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cubane
Manganese
manganese
trapping
chemistry
Jahn-Teller effect
Electrons
Alkalinity
valence
Methanol
Oxidation
Crystals
Molecules
Water
electrons
methyl alcohol
analogs
oxidation
shift
symmetry

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Trapping an elusive intermediate in manganese-oxo cubane chemistry. / Wu, Jian Zhong; Sellitto, Eric; Yap, Glenn P A; Sheats, John; Dismukes, G Charles.

In: Inorganic Chemistry, Vol. 43, No. 19, 20.09.2004, p. 5795-5797.

Research output: Contribution to journalArticle

Wu, Jian Zhong ; Sellitto, Eric ; Yap, Glenn P A ; Sheats, John ; Dismukes, G Charles. / Trapping an elusive intermediate in manganese-oxo cubane chemistry. In: Inorganic Chemistry. 2004 ; Vol. 43, No. 19. pp. 5795-5797.
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N2 - A new member of the Mn-oxo cubane core complex family [Mn 2III,2IV 4O4L6] (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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