Protic- or anionic-NHCs with a classical-NHC in a single [Ru(CNC)(PPh 3 ) 2 Cl]Cl pincer complex: direct comparison of structure & electronic properties and heterolytic H 2 splitting

Herein, we report the first set of pincer complexes 1 and 2 with the general formula [Ru(CNC)(PPh ) Cl]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...

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Published in:Dalton transactions : an international journal of inorganic chemistry 2024-04, Vol.53 (16), p.6870-6874
Main Authors: Srivastava, Navdeep, Singh, Amrendra K
Format: Article
Language:English
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Summary:Herein, we report the first set of pincer complexes 1 and 2 with the general formula [Ru(CNC)(PPh ) Cl]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 H gas at 1 atm pressure and 110 °C to give the Ru-hydride complex 3.
ISSN:1477-9226
1477-9234
DOI:10.1039/d4dt00623b