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Synergistic and Antagonistic Ligand Effects in the Transformation of Silver Compounds of Keto‐ and Cyano‐Functionalised Oximates and Nitronates: A Systematic Study Using Thermal Analysis
Author(s) -
Hoffmann Rudolf C.,
Schneider Jörg J.
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201500704
Subject(s) - chemistry , cyanoacetamide , malononitrile , nitroso , thermal decomposition , nitro , metal , intramolecular force , inorganic chemistry , redox , silver oxide , photochemistry , organic chemistry , catalysis , alkyl
Molecular silver compounds are target precursor molecules for the deposition of silver films from solution. The thermal decomposition of silver complexes of nitro and nitroso derivatives of malononitrile, cyanoacetamide and methyl cyanoacetate as well as with nitroacetamide and methyl nitroacetate was investigated for the first time in a systematic manner. The analysis of the evolving gases by means of infrared spectroscopy or mass spectrometry revealed that intramolecular redox reactions had a significant impact on the reaction mechanism, in particular the interactions of the nitro and nitroso functionalities with amido and ester groups. The studied ligands bearing cyano groups typically lead to the intermediary formation of silver cyanide, whereby metallic silver is formed only at higher temperatures. Silver complexes of nitroacetamide and methyl nitroacetate, however, undergo decomposition to metallic silver at temperatures already below 200 °C. Thin films of silver on glass substrates could be synthesised by spincoating of these precursors and subsequent annealing. Higher conversion temperatures lead to more uniform surface coverage and lower film roughness.