| Abstract |
The conversion of sterically unhindered organonitriles RCN (R=Me, Et, n-Pr, n-Bu) into the corresponding amidines RC(=NH)NH2, isolated as the nitrate salts, and carboxylic acids RCO2H proceeds in the appropriate nitrile as solvent in the presence of Co(NO3)(2). 6H(2)O or the cobalt(II) complex trans-[Co(MeCN)(2)(H2O)(4)](NO3)(2) and a ketoxime R C-2=NOH (R (2)=Me-2 or C5H10) but does not proceed at all with either the cobalt compound or the ketoxime taken alone. The amidinium nitrates were characterized by C, H, N elemental analyses, FAB(+)-MS, IR, H-1 and C-13\H-1\ NMR spectroscopies and the structures of RC(=NH2)NH2+NO3-(R=Et, n-Pr, n-Bu) were determined by X-ray crystallography, while the carboxylic acids were identified by GC and H-1 and C-13\H-1\ NMR spectroscopies. The reaction proceeds differently with sterically hindered organonitriles, e.g. i-PrCN and t-BuCN, and-instead of amidinium salts-ammonium nitrate and the appropriate carboxylic acids were identified. The structure of trans-[Co(MeCN)(2)(H2O)(4)](NO3)(2), which is anticipated to be an intermediate in the reaction of Co(NO3)(2). 6H(2)O, was determined by X-ray diffractometry. |
