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Synthesis of Platinum-nickel Nanowires and Optimization for Oxygen Reduction Performance
Published on: April 27, 2018
Synthesis and characterization of oxygen-functionalised-NHC silver(I) complexes and NHC transmetallation to
Sophie Hameury1, Pierre de Frémont, Pierre-Alain R Breuil
1Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, CS 90032, 67081 Strasbourg, France. braunstein@unistra.fr.
Abstract:
The new alcohol- and ether-functionalised-NHC silver(I) complexes bis(1-(2,6-diisopropylphenyl)-3-(2-hydroxyethyl)-1H-imidazol-2(3H)-ylidene)silver(I) chloride, [Ag{ImDiPP(C2OH)}2]Cl (4), bis(1-(2-hydroxyethyl)-3-mesityl-1H-imidazol-2(3H)-ylidene)silver(I) chloride, [Ag{ImMes(C2OH)}2]Cl (5), bis(1-(2-hydroxyethyl)-3-methyl-1H-imidazol-2(3H)-ylidene)silver(I) chloride, [Ag{ImMe(C2OH)}2]Cl (6), bis(1-(2,6-diisopropylphenyl)-3-(2-hydroxyethyl)-1H-imidazol-2(3H)-ylidene)silver(I) tetrafluoroborate, [Ag{ImDiPP(C2OH)}2]BF4 (9), and bis(1-(2,6-diisopropylphenyl)-3-(2-methoxyethyl)-1H-imidazol-2(3H)-ylidene)silver(I) chloride, [Ag{ImDiPP(C2OMe)}2]Cl (13), were synthesized and fully characterized by NMR spectroscopy and single crystal X-ray diffraction. For some complexes, an uncommon heteronuclear coupling (4)J((107/109)Ag-H) was unveiled. Their ability to transfer the NHC ligand to Ni(II) was assessed in the presence of different nickel(II) sources; the bis-NHC Ni(II) complex bis(1-(2,6-diisopropylphenyl)-3-(2-methoxyethyl)-1H-imidazol-2(3H)-ylidene)nickel(II) chloride, [NiCl2{ImDiPP(C2OMe)}2] (15), was obtained from 13 and shown by X-ray diffraction study to have a trans-arrangement of the two NHC ligands. However, in contrast to other Ag(I) NHC complexes the transmetallation reaction failed with the hydroxyl-functionalised silver complexes, possibly due to the acidity of the alcohol OH function, leading overall to reprotonation of the C(NHC) and isolation of the corresponding imidazolium salts.
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Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly,...