Cp*M2+ complexes (M = Rh, Ir; Cp* = C 5Me5) are described for 6-(carboxymethyl)-4-methyl-2- hydroxypyridine (cmhpH2), 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 (rO-O = 2.38 Å; 1H NMR δH 17.2), and (iii) Cp*Ir(cmhpH)Cl efficiently catalyzes the dehydrogenation of PhCH(OH)Me to PhC(O)Me.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry