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. (2009) Structural and Catalytic Characterization of a Heterovalent Mn(II)Mn(III) Complex That Mimics Purple Acid Phosphatases. Inorganic Chemistry, 48. pp. 10036-10048. ISSN 0020-1669
Download (2MB)
|
Abstract
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.
Item Type: | Article |
---|---|
Additional Information: | The definitive version of this article is available In Inorganic Chemistry, 2009, 48, 10036–10048. DOI: 10.1021/ic9005086 . ©2009 American Chemical Society |
Keywords: | Structural; Catalytic Characterization; Heterovalent; Mn(II)Mn(III); Purple Acid Phosphatases; |
Academic Unit: | Faculty of Science and Engineering > Chemistry |
Item ID: | 3726 |
Depositing User: | Gary Schenk |
Date Deposited: | 06 Jun 2012 07:40 |
Journal or Publication Title: | Inorganic Chemistry |
Publisher: | American Chemical Society |
Refereed: | Yes |
URI: | |
Use Licence: | This item is available under a Creative Commons Attribution Non Commercial Share Alike Licence (CC BY-NC-SA). Details of this licence are available here |
Repository Staff Only(login required)
Item control page |
Downloads
Downloads per month over past year