Smith, Sarah J. and Riley, Mark J. and Noble, Christopher J. and Hanson, Graeme R. and Stranger, Robert and Jayaratne, Vidura and Cavigliasso, German and Schenk, Gerhard and Gahan, Lawrence R.
Structural and Catalytic Characterization of a Heterovalent Mn(II)Mn(III) Complex
That Mimics Purple Acid Phosphatases.
Inorganic Chemistry, 48.
The binuclear heterovalent manganese model complex [Mn(II)Mn(III)(L1)(OAc)2] ClO4 3 H2O (H2L1 = 2-(((3-((bis-
(pyridin-2-ylmethyl)amino)methyl)-2-hydroxy-5-methylbenzyl)(pyridin-2-ylmethyl)amino)-methyl)phenol) has been prepared
and studied structurally, spectroscopically, and computationally. The magnetic and electronic properties of the
complex have been related to its structure. The complex is weakly antiferromagnetically coupled (J ∼ -5 cm-1,
H =-2J S1 3 S2) and the electron paramagnetic resonance (EPR) and magnetic circular dichroism (MCD) spectra identify
the Jahn-Teller distortion of the Mn(III) center as predominantly a tetragonal compression, with a significant rhombic
component. Electronic structure calculations using density functional theory have confirmed the conclusions derived from
the experimental investigations. In contrast to isostructural M(II)Fe(III) complexes (M = Fe, Mn, Zn, Ni), theMn(II)Mn(III)
system is bifunctional possessing both catalase and hydrolase activities, and only one catalytically relevant pKa (= 8.2) is
detected. Mechanistic implications are discussed.
||The definitive version of this article is available In Inorganic Chemistry, 2009, 48, 10036–10048.
DOI: 10.1021/ic9005086 . ©2009 American Chemical Society
||Structural; Catalytic Characterization; Heterovalent; Mn(II)Mn(III); Purple Acid Phosphatases;
||Faculty of Science and Engineering > Chemistry
||06 Jun 2012 07:40
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