RESUMO
Herein, we report the first set of pincer complexes 1 and 2 with the general formula [Ru(CNC)(PPh3)2Cl]Cl having a protic- and classical-NHC in the same molecule and nearly identical environments. Deprotonation of the protic-NHC complex 2 with one equivalent of base leads to the formation of anionic-NHC complex 2'. These complexes allow a direct comparison of protic- and anionic-NHCs with the classical-NHC ligand. A comparison of the molecular structure indicated that the metal carbene bond length trend is anionic-NHC > protic-NHC > classical-NHC. The electrochemical investigation revealed the electron donation tendency is classical-NHC > protic-NHC and anionic-NHC > protic-NHC. Cooperation between the metal and the ligand is indicated by the reaction of 2' with H2 gas at 1 atm pressure and 110 °C to give the Ru-hydride complex 3.
RESUMO
A series of Ru(III)-NHC complexes, identified as [RuIII(PyNHCR)(Cl)3(H2O)] (1a-c), have been prepared, starting from RuCl3·3H2O following a base-free route. The Lewis acidic Ru(III) centre operates via a halide-assisted, electrophilic C-H activation for carbene generation. The best results were obtained with azolium salts having the I- anion, while ligand precursors with Cl-, BF4-, and PF6- gave no complex formation and those with Br- gave a product with mixed halides. The structurally simple, air and moisture-stable complexes represent rare examples of paramagnetic Ru(III)-NHC complexes. Furthermore, these benchtop stable Ru(III)-NHC complexes were shown to be excellent metal precursors for the synthesis of new [RuII(PyNHCR)(Cl)2(PPh3)2] (2a-c) and [RuII(PyNHCR)(CNCMe)I]PF6 (3a-c) complexes. All the complexes have been characterised using spectroscopic methods, and the structures of 1a, 1b, 2c, and 3a have been determined using the single-crystal X-ray diffraction technique. This work allows easy access to new Ru-NHC complexes for the study of new properties and novel applications.
