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

Aaron M. Royer, Thomas B. Rauchfuss, Scott R. Wilson

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

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 (r_O-O = 2.38 Å; ¹H NMR δ_H 17.2), and (iii) Cp*Ir(cmhpH)Cl efficiently catalyzes the dehydrogenation of PhCH(OH)Me to PhC(O)Me.

Original language	English (US)
Pages (from-to)	395-397
Number of pages	3
Journal	Inorganic Chemistry
Volume	47
Issue number	2
DOIs	https://doi.org/10.1021/ic7018692
State	Published - Jan 21 2008

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Coordination chemistry of a model for the GP cofactor in the hmd hydrogenase: Hydrogen-bonding and hydrogen-transfer catalysis",

abstract = "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 {\AA}; 1H NMR δH 17.2), and (iii) Cp*Ir(cmhpH)Cl efficiently catalyzes the dehydrogenation of PhCH(OH)Me to PhC(O)Me.",

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T1 - Coordination chemistry of a model for the GP cofactor in the hmd hydrogenase

T2 - Hydrogen-bonding and hydrogen-transfer catalysis

AU - Royer, Aaron M.

AU - Rauchfuss, Thomas B.

AU - Wilson, Scott R.

PY - 2008/1/21

Y1 - 2008/1/21

N2 - 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.

AB - 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.

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

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