Maynooth University

Maynooth University ePrints and eTheses Archive

Maynooth University Library

Structural and Catalytic Characterization of a Heterovalent Mn(II)Mn(III) Complex That Mimics Purple Acid Phosphatases

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

[img] 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;
Subjects: Science & 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:

Repository Staff Only(login required)

View Item Item control page

Document Downloads

More statistics for this item...