Issue 19, 2015

Decarboxylation and simultaneous reduction of silver(i) β-ketocarboxylates with three types of coordinations

Abstract

A series of silver(I) β-ketocarboxylates were prepared by reaction of β-ketocarboxylic acids with silver nitrate in the presence of diethanolamine. The silver(I) β-ketocarboxylates decomposed over a narrow temperature range to form metallic silver, CO2, and the corresponding ketones. In addition, products derived from radical intermediates were detected by mass spectroscopic analysis for some silver(I) β-ketocarboxylates. Infrared and solid state 13C-NMR spectra of silver(I) β-ketocarboxylates suggested the presence of two types of structures involving a carbonyl group in addition to the dimeric eight-membered ring structure as in the structure of silver(I) stearate. The silver(I) β-ketocarboxylate model compound used was HCOCH2COOAg and its structures were determined using density functional theory (DFT) and atoms-in-molecules (AIM) methods. Three types of coordinations around the Ag ion differing significantly in Ag–O bond strengths were found. Based on the calculated structures and experimental results, the relationships between the structures and decomposition temperatures are discussed in terms of the thermal decomposition process.

Graphical abstract: Decarboxylation and simultaneous reduction of silver(i) β-ketocarboxylates with three types of coordinations

Supplementary files

Article information

Article type
Paper
Submitted
23 Feb 2015
Accepted
01 Apr 2015
First published
02 Apr 2015

Dalton Trans., 2015,44, 8993-9003

Author version available

Decarboxylation and simultaneous reduction of silver(I) β-ketocarboxylates with three types of coordinations

M. Hatamura, S. Yamaguchi, S. Takane, Y. Chen and K. Suganuma, Dalton Trans., 2015, 44, 8993 DOI: 10.1039/C5DT00773A

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