Synthetic, spectroscopic and structural behavior of unsaturated functionalized N-heterocyclic carbene complexes of group 11

• Published in: Polyhedron 2017-11, Vol.137, p.97-111
• Main Authors: González-Abrego, Daniel Omar, Zuno-Cruz, Francisco J., Carpio-Granillo, Mariana, Andrade-López, Noemí, Cruz-Borbolla, Julián, Martínez-Macias, Claudia, Mendoza-Espinosa, Daniel, Rosales-Hoz, María J., Leyva, Marco A., Torres-Lubián, José R., López-Jiménez, Jorge A., Jancik, Vojtech, Sánchez-Cabrera, Gloria
• Format: Article
• Language: English
• Subjects: Copper; Gold; Imidazolium salts; Silver; Unsaturated NHC
• ISSN: 0277-5387
• DOI: 10.1016/j.poly.2017.08.012

A series of unsaturated functionalized silver(I) N-heterocyclic carbenes [{(κC-C7N2H10)AgCl}2] (1a), [{(κC-C8N2H12)2}2Ag][Ag2Cl4] (1b), [{(κC-C9N2H14)2Ag}2][Ag2Cl4] (1c), and [{(κC-C12N2H14)2Ag}2][Ag2Cl4] (1d) have been synthesized and studied as transmetalation agents onto [Au(SMe2)Cl] and CuI. The transmetalation reactions produced the mixed-metal biscarbene compounds, [(κC-C7N2H10)2M][AgCl2] (M=Au 2a; Cu 3a), [{(κC-C8N2H12)2}2M][Ag2Cl4] (M=Au 2b; Cu 3b), [{(κC-C9N2H14)2M}2][Ag2Cl4] (M=Au 2c; Cu 3c), and [{(κC-C12N2H14)2}2M][Ag2Cl4] (M=Au 2d; Cu 3d). The carbene complexes were fully characterized by IR, NMR, mass spectrometry, and the molecular structures of 1a, 1b, 2b and the imidazolium salt [PMIM][PF6] (L2′) were determined by single crystal X-ray diffraction studies. Compounds L4, 1d and 2d were used as monomeric units to carry out free-radical polymerization (FRP) reactions using AIBN as initiator. [Display omitted] A series of unsaturated functionalized silver(I) N-heterocyclic carbenes [{(κC-C7N2H10)AgCl}2] (1a), [{(κC-C8N2H12)2}2Ag][Ag2Cl4] (1b), [{(κC-C9N2H14)2Ag}2][Ag2Cl4] (1c), and [{(κC-C12N2H14)2Ag}2][Ag2Cl4] (1d) have been synthesized and used as transmetalation agents to form the corresponding Au(I) and Cu(I) complexes. The reactions of 1a-d with [Au(SMe2)Cl] or CuI produced the mixed-metal biscarbene compounds [(κC-C7N2H10)2M][AgCl2] (M=Au 2a; Cu 3a), [{(κC-C8N2H12)2}2M][Ag2Cl4] (M=Au 2b; Cu 3b), [{(κC-C9N2H14)2M}2][Ag2Cl4] (M=Au 2c; Cu 3c), and [{(κC-C12N2H14)2}2M][Ag2Cl4] (M=Au 2d; Cu 3d). The carbene complexes were fully characterized by IR, NMR and mass spectrometry, and the molecular structures of 1a, 1b, 2b and the imidazolium salt [PMIM][PF6] (L2′) were determined by single crystal X-ray diffraction studies. Compounds L4, 1d and 2d were used as monomeric units to carry out free-radical polymerization (FRP) reactions using AIBN as initiator.