On Copper(I) Fluorides,the Cuprophilic Interaction,the Preparation of Copper Nitride at Room Temperature,and the Formation Mechanism at Elevated Temperatures |
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| Authors: | Dipl‐Chem Patrick Woidy Dr Antti J Karttunen Dr Marc Widenmeyer Prof?Dr Rainer Niewa Prof?Dr Florian Kraus |
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| Affiliation: | 1. Fachbereich Chemie, Philipps‐Universit?t Marburg, Hans‐Meerwein‐Strasse 4, 35032 Marburg (Germany) http://www.uni‐marburg.de/fb15/ag‐kraus/;2. Department of Chemistry, Aalto University, 00076 Aalto (Finland);3. Institute of Inorganic Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart (Germany);4. Current address: Institute for Materials Science, University of Stuttgart, Heisenbergstrasse 3, 70569 Stuttgart (Germany) |
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| Abstract: | Our attempts to synthesize the hitherto unknown binary copper(I) fluoride have led to first successes and a serendipitious result: By conproportionation of elemental copper and copper(II) fluoride in anhydrous liquid ammonia, two copper(I) fluorides were obtained as simple NH3 complexes. One of them presents an example of ligand‐unsupported “cuprophilic” interactions in an infinite Cu2(NH3)4]2+ chain with alternating Cu–Cu distances. We discovered that both copper(I) fluorides can easily be converted into Cu3N at room temperature, just by applying a vacuum. Additionally, we investigated the formation mechanism of the classical synthesis route of Cu3N that starts with CuF2 and flowing NH3 in the temperature range between ambient and 290 °C by means of thermal analysis and in situ neutron diffraction. The reaction proceeds at elevated temperatures through the formation of a blue and amorphous ammoniate Cu(NH3)2F2, the reformation of CuF2, and finally the redox reaction to form Cu3N. |
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| Keywords: | copper cuprophilic interactions fluorides nitrides structure elucidation |
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