title: 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 (13)C-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.
authors.affiliation: The Institute of Scientific and Industrial Research, Osaka University, 8-1 Mihogaoka, Ibaraki, Osaka 567-0047, Japan. hatamura@sanken.osaka-u.ac.jp.
authors.forename: Mariko
authors.initials: M
authors.lastname: Hatamura
authors.forename: Shunro
authors.initials: S
authors.lastname: Yamaguchi
authors.forename: Shin-ya
authors.initials: SY
authors.lastname: Takane
authors.forename: Yu
authors.initials: Y
authors.lastname: Chen
authors.forename: Katuaki
authors.initials: K
authors.lastname: Suganuma