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Updated: May 15, 2025

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
Syntheses and crystal structures of 4-benzyl-1-ethyl-1,2,4-triazolium bromide and its corresponding NHC complexes of
Timothy G Lerch1, Daniel R Albert1, Michael Gau2
1Department of Chemistry Millersville University,Millersville PA 17551 USA.
Abstract:
The syntheses and crystal structures of a triazolium salt, 4-benzyl-1-ethyl-1,2,4-triazolium bromide, C11H14N3 +·Br- (2), and the corresponding N-heterocyclic carbene complexes, (4-benzyl-1-ethyl-1,2,4-triazol-5-yl-idene)chlorido-[(1,2,5,6-η)-cyclo-octa-1,5-diene]rhodium(I), [RhCl(C8H12)(C11H13N3)] (3), (4-benzyl-1-ethyl-1,2,4-triazol-5-yl-idene)[(1,2,5,6-η)-cyclo-octa-1,5-diene](tri-phenyl-phosphane)iridium(I) tetra-fluorido-borate, [Ir(C8H12)(C11H13N3)(C18H15P)]BF4 (5), and (4-benzyl-1-ethyl-1,2,4-triazol-5-yl-idene)[(1,2,5,6-η)-cyclo-octa-1,5-diene](tri-cyclo-hexyl-phosphane)iridium(I) tetra-fluorido-borate dicholoro-methane sesquisolvate, [Ir(C8H12)(C11H13N3)(C18H33P)]BF4·1.5CH2Cl2 (6), are presented. Complexes 2 and 6 crystallize in the monoclinic space group P21/c, complex 3 in the triclinic space group P1 and complex 5 in the triclinic space group P1 with two mol-ecules in the asymmetric unit. The three metal complexes 3, 5, and 6 have a distorted square-planar geometry around the metal ions. The N1-C1-N3 bond angle in the triazolium salt 2 is 107.1 (2)° and is observed in the range of 102.2 (3) to 103.8 (5)° in the NHC ligands in complexes 3, 5, and 6. The two substituent 'wing tips' in the NHC ligand (N-ethyl and N-benz-yl) are oriented in an anti-arrangement in compounds 2 and 3, a syn-arrangement in compound 6, and both syn and anti-arrangements in the two independent ion pairs in compound 5. All structures exhibit non-classical hydrogen-bonding inter-actions with the most acidic hydrogen atoms in complexes 2 and 3 playing critical roles in the orientations of structural units.
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