Reactions of hydroxymethyl and hydride complexes in water

Synthesis, structure and reactivity of a hydroxymethyl-cobalt complex

Carol Creutz, Mei H. Chou, Etsuko Fujita, David J. Szalda

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

The properties and reactions of hydroxymethyl and hydride complexes are surveyed with an emphasis on their aqueous chemistry; then the syntheses and reactions found for macrocyclic cobalt complexes of these ligands are presented. The hydroxymethyl-cobalt(III) complex was prepared by addition of the photogenerated CH 2OH radical to the cobalt(II) macrocycle N-meso-CoHMD 2+ (HMD = 5,7,7,12,14,14-hexamethyl-1,4,8,11- tetraazacyclotetradeca-4,11-diene) in 0.1 M perchloric acid and characterized by an X-ray crystallographic study and spectroscopic characterization in solution. Acidic aqueous solutions are fairly stable and the complex decomposes, with formaldehyde elimination, by a base-catalyzed pathway. At 25°C, formaldehyde elimination proceeds with the rate law -d[N-meso-CoHMD(CH 2OH) 2+]/dt = k I[N-meso-CoHMD(CH 2OH) 2+]/[H +], with k I = (3.5 ± 0.5) × 10 -9 M s -1 at pH 4-7 and 0.5 M ionic strength to yield the hydride complex, N-meso-CoHMD(H) 2+ and CH 2O. In a subsequent stage, N-meso-CoHMD 2+ and H 2 form with the rate law -d[N-meso-CoHMD(H) 2+]/dt = (2 ± 1) × 10 -7 [N-meso-CoHMD(H) 2+] 2/[H +] s -1 at pH 4.5-8 and 0.5 M ionic strength. Ultimately, the N-meso complex isomerizes to yield N-rac-CoHMD 2+ with previously observed kinetics.

Original languageEnglish
Pages (from-to)375-390
Number of pages16
JournalCoordination Chemistry Reviews
Volume249
Issue number3-4 SPEC. ISS.
DOIs
Publication statusPublished - Feb 2005

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Cobalt
Hydrides
hydrides
cobalt
reactivity
methylidyne
Ionic strength
Formaldehyde
Water
synthesis
formaldehyde
water
Helmet mounted displays
elimination
helmet mounted displays
perchloric acid
dienes
Ligands
X rays
Hydrogen

Keywords

  • Hydride complex
  • Hydroxymethyl complex
  • Water reduction mechanism

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Reactions of hydroxymethyl and hydride complexes in water : Synthesis, structure and reactivity of a hydroxymethyl-cobalt complex. / Creutz, Carol; Chou, Mei H.; Fujita, Etsuko; Szalda, David J.

In: Coordination Chemistry Reviews, Vol. 249, No. 3-4 SPEC. ISS., 02.2005, p. 375-390.

Research output: Contribution to journalArticle

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abstract = "The properties and reactions of hydroxymethyl and hydride complexes are surveyed with an emphasis on their aqueous chemistry; then the syntheses and reactions found for macrocyclic cobalt complexes of these ligands are presented. The hydroxymethyl-cobalt(III) complex was prepared by addition of the photogenerated CH 2OH radical to the cobalt(II) macrocycle N-meso-CoHMD 2+ (HMD = 5,7,7,12,14,14-hexamethyl-1,4,8,11- tetraazacyclotetradeca-4,11-diene) in 0.1 M perchloric acid and characterized by an X-ray crystallographic study and spectroscopic characterization in solution. Acidic aqueous solutions are fairly stable and the complex decomposes, with formaldehyde elimination, by a base-catalyzed pathway. At 25°C, formaldehyde elimination proceeds with the rate law -d[N-meso-CoHMD(CH 2OH) 2+]/dt = k I[N-meso-CoHMD(CH 2OH) 2+]/[H +], with k I = (3.5 ± 0.5) × 10 -9 M s -1 at pH 4-7 and 0.5 M ionic strength to yield the hydride complex, N-meso-CoHMD(H) 2+ and CH 2O. In a subsequent stage, N-meso-CoHMD 2+ and H 2 form with the rate law -d[N-meso-CoHMD(H) 2+]/dt = (2 ± 1) × 10 -7 [N-meso-CoHMD(H) 2+] 2/[H +] s -1 at pH 4.5-8 and 0.5 M ionic strength. Ultimately, the N-meso complex isomerizes to yield N-rac-CoHMD 2+ with previously observed kinetics.",
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N2 - The properties and reactions of hydroxymethyl and hydride complexes are surveyed with an emphasis on their aqueous chemistry; then the syntheses and reactions found for macrocyclic cobalt complexes of these ligands are presented. The hydroxymethyl-cobalt(III) complex was prepared by addition of the photogenerated CH 2OH radical to the cobalt(II) macrocycle N-meso-CoHMD 2+ (HMD = 5,7,7,12,14,14-hexamethyl-1,4,8,11- tetraazacyclotetradeca-4,11-diene) in 0.1 M perchloric acid and characterized by an X-ray crystallographic study and spectroscopic characterization in solution. Acidic aqueous solutions are fairly stable and the complex decomposes, with formaldehyde elimination, by a base-catalyzed pathway. At 25°C, formaldehyde elimination proceeds with the rate law -d[N-meso-CoHMD(CH 2OH) 2+]/dt = k I[N-meso-CoHMD(CH 2OH) 2+]/[H +], with k I = (3.5 ± 0.5) × 10 -9 M s -1 at pH 4-7 and 0.5 M ionic strength to yield the hydride complex, N-meso-CoHMD(H) 2+ and CH 2O. In a subsequent stage, N-meso-CoHMD 2+ and H 2 form with the rate law -d[N-meso-CoHMD(H) 2+]/dt = (2 ± 1) × 10 -7 [N-meso-CoHMD(H) 2+] 2/[H +] s -1 at pH 4.5-8 and 0.5 M ionic strength. Ultimately, the N-meso complex isomerizes to yield N-rac-CoHMD 2+ with previously observed kinetics.

AB - The properties and reactions of hydroxymethyl and hydride complexes are surveyed with an emphasis on their aqueous chemistry; then the syntheses and reactions found for macrocyclic cobalt complexes of these ligands are presented. The hydroxymethyl-cobalt(III) complex was prepared by addition of the photogenerated CH 2OH radical to the cobalt(II) macrocycle N-meso-CoHMD 2+ (HMD = 5,7,7,12,14,14-hexamethyl-1,4,8,11- tetraazacyclotetradeca-4,11-diene) in 0.1 M perchloric acid and characterized by an X-ray crystallographic study and spectroscopic characterization in solution. Acidic aqueous solutions are fairly stable and the complex decomposes, with formaldehyde elimination, by a base-catalyzed pathway. At 25°C, formaldehyde elimination proceeds with the rate law -d[N-meso-CoHMD(CH 2OH) 2+]/dt = k I[N-meso-CoHMD(CH 2OH) 2+]/[H +], with k I = (3.5 ± 0.5) × 10 -9 M s -1 at pH 4-7 and 0.5 M ionic strength to yield the hydride complex, N-meso-CoHMD(H) 2+ and CH 2O. In a subsequent stage, N-meso-CoHMD 2+ and H 2 form with the rate law -d[N-meso-CoHMD(H) 2+]/dt = (2 ± 1) × 10 -7 [N-meso-CoHMD(H) 2+] 2/[H +] s -1 at pH 4.5-8 and 0.5 M ionic strength. Ultimately, the N-meso complex isomerizes to yield N-rac-CoHMD 2+ with previously observed kinetics.

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