Journal
INORGANIC CHEMISTRY
Volume 43, Issue 19, Pages 5795-5797Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic048988b
Keywords
-
Categories
Funding
- NIGMS NIH HHS [GM-39932] Funding Source: Medline
Ask authors/readers for more resources
A new member of the Mn-oxo cubane core complex family [Mn(4)(2III,2IV)O(4)L(6)] (1), where L = (p-MeOPh)(2)PO(2)(-), 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(2)PO(2)(-). 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) (4)O(2)(OMe)(2)(MeOH){(p-MeOph)(2)PO(2)}(6)] (2). Each Will of 2 is tetragonally distorted due to the Jahn-Teller effect with elongated Mn-O bonds that are directed at the two mu(3)-MeO bridges and neither of the two mu(3)-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.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available