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 language | English |
|---|---|
| Pages (from-to) | 5795-5797 |
| Number of pages | 3 |
| Journal | Inorganic Chemistry |
| Volume | 43 |
| Issue number | 19 |
| DOIs | |
| Publication status | Published - Sep 20 2004 |
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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 journal › Article
}
TY - JOUR
T1 - Trapping an elusive intermediate in manganese-oxo cubane chemistry
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,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.
AB - 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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U2 - 10.1021/ic048988b
DO - 10.1021/ic048988b
M3 - Article
C2 - 15360226
AN - SCOPUS:4644335026
VL - 43
SP - 5795
EP - 5797
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 19
ER -