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Dalton Trans. 2014 Apr 21;43(15):5847-57. doi: 10.1039/c3dt53352b. Epub 2014 Feb 28.

Anion exchange in [Ni(η(5)-C(5)H(4)R)(Cl)(NHC)]. Counterion effect on the structure and catalytic activity.

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  • 1Warsaw University of Technology, Faculty of Chemistry, Noakowskiego 3, 00-664 Warsaw, Poland.


A series of novel complexes [Ni(η(5)-C5H4R)(L)(NHC)](+)A(-)2a-2j and [Ni(η(5)-C5H5)(A)(NHC)] 3a-3c has been obtained by anion metathesis from the corresponding chlorides 1a-1d, depending on the anion binding properties and reaction conditions. Solid-state structures of two cationic complexes (2c, 2j) and two complexes with a coordinated anion (3a, 3c) have been determined by X-ray diffraction revealing a trigonal planar geometry in all cases. Unexpectedly, 3c displayed unprecedented for this type of compounds temperature-dependent NMR spectra that were interpreted in terms of spin equilibrium. The cationic complexes 2 were less efficient in styrene polymerization than the parent chlorides 1. However, the activity of 2 and 3 in Suzuki cross-coupling did not depend considerably on the counterion.

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