Coordination chemistry of a model for the GP cofactor in the Hmd hydrogenase: hydrogen-bonding and hydrogen-transfer catalysis

Aaron M Royer; Thomas B Rauchfuss; Scott R Wilson

doi:10.1021/ic7018692

Coordination chemistry of a model for the GP cofactor in the Hmd hydrogenase: hydrogen-bonding and hydrogen-transfer catalysis

Inorg Chem. 2008 Jan 21;47(2):395-7. doi: 10.1021/ic7018692. Epub 2007 Dec 15.

Authors

Aaron M Royer¹, Thomas B Rauchfuss, Scott R Wilson

Affiliation

¹ Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA.

PMID: 18081276
DOI: 10.1021/ic7018692

Abstract

Cp(*)M(2+) complexes (M = Rh, Ir; Cp(*) = C(5)Me(5)) are described for 6-(carboxymethyl)-4-methyl-2-hydroxypyridine (cmhpH(2)), an analogue of the guanylylpyridone cofactor in the hydrogenase Hmd. Three findings indicate that Cp(*)M(Hcmhp)(+) stabilizes the binding of hydrogen-bond acceptors to the sixth coordination site: (i) water binds in preference to Cl-, (ii) the adduct Cp(*)Rh(cmhp)(2-hydroxypyridine) exhibits a very short intramolecular hydrogen bond (r(o-o) = 2.38 A; (1)H NMR delta(H) 17.2), and (iii) Cp(*)Ir(cmhpH)Cl efficiently catalyzes the dehydrogenation of PhCH(OH)Me to PhC(O)Me.

Publication types

Research Support, N.I.H., Extramural
Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

Catalysis
Hydrogen Bonding
Hydrogenase / chemistry*
Models, Molecular*

Substances

Hydrogenase