Synthesis, Characterization, and Structural Transformation of Picolyl-Functionalized Polynuclear Silver(I)– and Gold(I)–N-Heterocyclic Carbene Complexes

Abstract

Three coinage-metal (AgI, CuI, and AuI) NHC complexes featuring picolyl-functionalized NHC ligands were synthesized and fully characterized by NMR spectroscopy and single-crystal X-ray diffraction analyses. The obtained complexes exhibit different geometries depending on the diversified coordination modes of the multidentate ligand toward different metal ions. The trinuclear AgI complex [Ag3(L)2]­(PF6)3 was directly synthesized by the one-step reaction of picolyl-functionalized diimidazolium salts with Ag2O. Further, transmetalation of [Ag3 L 2]­(PF6)3 with CuCl and Au­(THT)Cl (THT = tetrahydrothiophene) led to the formation of the unexpected copper­(I)–NHC complex {[CuL(CH3CN)­Cl]­PF6} n with one-dimensional chain structure and the tetranuclear gold­(I) complex [Au4 L 2]­Cl­(PF6)3, respectively. Interestingly, the two trinuclear AuI–NHC complexes [Au3 L 2]2(2,6-nds)3 and [Au3 L 2]2(1,5-nds)3 (nds = naphthalenedisulfonate) were further obtained through an anion-induced structural transformation of [Au4 L 2]­Cl­(PF6)3. Complexes [Au3 L 2]2(2,6-nds)3 and [Au3 L 2]2(1,5-nds)3 were also characterized by mass spectrometry and single-crystal X-ray diffraction studies.

Ftalimit Sübstitüe Ag(I) NHC Komplekslerinin Sentez ve Karakterizasyonu

“…Bu konumlara eklenen ligantlar yapıya çözünürlük kazandırabilmesinin yanısıra sterik etki oluşturabilmesine de olanak sağlamaktadır. Karbenler periyodik tablodaki iç geçiş elementlerinin çoğu ile kompleks oluşturabilmektedir [3][4][5][6][7][8][9]. Literatüre baktığımızda Ag, Au, Cu, Co, Fe, Ir, Pd, Pt, Ru, Rh karben komplekslerinin hala yoğun bir şekilde çalışılmakta olduğunu görmekteyiz.…”