Tripodal Tris-tacn and Tris-DPA Platforms for Assembling Phosphate-Templated Trimetallic Centers
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Cao et al JACS.pdf
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1.61 MB
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Author(s)
Cao, Rui
Mueller, Peter
Lippard, Stephen J.
Date Issued
November 2010
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society
Citation
Cao, Rui, Peter Müller, and Stephen J. Lippard. “Tripodal Tris-tacn and Tris-dpa Platforms for Assembling Phosphate-Templated Trimetallic Centers.” Journal of the American Chemical Society 132.49 (2010): 17366-17369.
Version
Author's final manuscript
Abstract
Multidentate tripodal ligands, N(CH2-m-C6H4-CH2tacn)3 (L1) and N(CH2-o-C6H4-CH2N(CH2py)2)3 (L2), have been devised for assembling high-nuclearity metal clusters. By using the same tripodal platform with different ligand appendages, either triazacyclononanes or dipicolylamines, and functionalizing either the ortho or the meta positions on the tris(xylyl) linker arms, discrete trimetal phosphate units of relevance to phosphate-metabolizing trimetallic centers in biology were prepared. Four such compounds, [(CuIICl)3(HPO4)L1](PF6) (1), [(CuIICl)3(HAsO4)L1](PF6) (2), Na2[MnIII6MnII2(H2O)2(HPO4)6(PO4)4(L1)2] (3), and [CoII3(H2PO4)Cl2(MeCN)L2](PF6)3 (4), all containing three metal centers bound to a central phosphate or arsenate unit bridging oxygen atoms, have been synthesized and structurally characterized. These results demonstrate the propensity of this novel tripodal ligand platform, in the presence of phosphate or arsenate, to assemble {M3(EO4)} units and thus structurally mimic trimetallic active sites of proteins involved in phosphate metabolism. Reactivity studies reveal that the tricopper complex 1 is more efficient than monocopper analogues in catalyzing the hydrolysis of 4-nitrophenyl phosphate.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/ja108212v
