Homoleptic Gold Acetonitrile Complexes with Medium to Very Weakly Coordinating Counterions: Effect on Aurophilicity?
| Autor: | Ingo Krossing, Daniel Kratzert, Przemysław J. Malinowski, Christian Friedmann, Arthur Martens, Tobias A. Engesser |
|---|---|
| Rok vydání: | 2016 |
| Předmět: |
chemistry.chemical_classification
010405 organic chemistry Stereochemistry Ligand Organic Chemistry General Chemistry Nuclear magnetic resonance spectroscopy Crystal structure 010402 general chemistry 01 natural sciences Aurophilicity Catalysis 0104 chemical sciences chemistry.chemical_compound Crystallography chemistry Reactivity (chemistry) Counterion Homoleptic Acetonitrile |
| Zdroj: | Chemistry - A European Journal. 22:15085-15094 |
| ISSN: | 0947-6539 |
| Popis: | A series of gold acetonitrile complexes [Au(NCMe)2 ]+ [WCA]- with weakly coordinating counterions (WCAs) was synthesized by the reaction of elemental gold and nitrosyl salts [NO]+ [WCA]- in acetonitrile ([WCA]- =[GaCl4 ]- , [B(CF3 )4 ]- , [Al(ORF )4 ]- ; RF =C(CF3 )3 ). In the crystal structures, the [Au(NCMe)2 ]+ units appeared as monomers, dimers, or chains. A clear correlation between the aurophilicity and the coordinating ability of counterions was observed, with more strongly coordinating WCAs leading to stronger aurophilic contacts (distances, C-N stretching frequencies of [Au(NCMe)2 ]+ units). An attempt to prepare [Au(L)2 ]+ units, even with less weakly basic solvents like CH2 Cl2 , led to decomposition of the [Al(ORF )4 ]- anion and formation of [NO(CH2 Cl2 )2 ]+ [F(Al(ORF )3 )2 ]- . All nitrosyl reagents [NO]+ [WCA]- were generated according to an optimized procedure and were thoroughly characterized by Raman and NMR spectroscopy. Moreover, the to date unknown species [NO]+ [B(CF3 )3 CN]- was prepared. Its reaction with gold unexpectedly produced [Au(NCMe)2 ]+ [Au(NCB(CF3 )3 )2 ]- , in which the cyanoborate counterion acts as an anionic ligand itself. Interestingly, the auroborate anion [Au(NCB(CF3 )3 )2 ]- behaves as a weakly coordinating counterion, which becomes evident from the crystallographic data and the vibrational spectral characteristics of the [Au(NCMe)2 ]+ cation in this complex. Ligand exchange in the only room temperature stable salt of this series, [Au(NCMe)2 ]+ [Al(ORF )4 ]- , is facile and, for example, [Au(PPh3 )(NCMe)]+ [Al(ORF )4 ]- can be selectively generated. This reactivity opens the possibility to generate various [AuL1 L2 ]+ [Al(ORF )4 ]- salts through consecutive ligand-exchange reactions that offer access to a huge variety of AuI complexes for gold catalysis. |
| Databáze: | OpenAIRE |
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