Luminescent Gold(I) Carbenes from 2-Pyridylisocyanide Complexes: Structural Consequences of Intramolecular versus Intermolecular Hydrogen-Bonding Interactions

Abstract

Isocyanide [AuX(CNPy-2)] (X = Cl, C6F5, fluoromesityl, 1/2 octafluorobiphenyl) and carbene [AuX{C(NR1R2)(NHPy-2)}] (R1R2NH = primary or secondary amines or 1/2 primary diamine) gold(I) complexes have been synthesized and characterized. For X = Cl, the carbene complexes show aurophilic interactions. The fragment NHPy-2, formed in the carbenes, can give rise to intra- (for primary amines) or intermolecular (for secondary amines) hydrogen bonds, depending on the amine used. These bonds and contacts have been studied in the solid state and in solution. The intermolecular hydrogen bonds are split in an acetone solution, but the intramolecular ones, which close a six-membered ring, survive in solution. Except for the fluoromesityl derivatives, the carbene complexes display luminescent properties.

New and Easily Accessible Nitrogen Acyclic Gold(I) Carbenes: Structure and Application in the Gold‐Catalyzed Phenol Synthesis as well as the Hydration of Alkynes

“…Two years later the same authors also reported the synthesis of the first five nitrogen acyclic carbene (NAC, Figure 2) complexes of gold by addition of primary amines to isonitrilegold chloro complexes. [11] Applications of the isonitrile and NAC gold complexes in the field of luminiscent compounds, [12] laser-induced writing with gold on ceramic surfaces, [13] liquid crystals [14] and water-soluble complexes [14] have been reported. The first NHC complex of gold(I) was prepared in 1989, [15] and at present these gold carbene complexes are the dominating car- …”

Synthesis and Catalytic Activity of Gold Chiral Nitrogen Acyclic Carbenes and Gold Hydrogen Bonded Heterocyclic Carbenes in Cyclopropanation of Vinyl Arenes and in Intramolecular Hydroalkoxylation of Allenes

“…5 We have recently reported that gold(I) complexes with other types of carbene ligands, that we have named HBHCs (hydrogen bonded heterocyclic carbenes, e.g., [AuCl{C(NRH)(NHPy-2)}]), or NAC (nitrogen acyclic carbenes, e.g., [AuCl{C(NHR)(NHR 0 )}] or [AuCl{C(NHR)(NR 0 2 )}]), are good catalysts in skeletal rearrangement and in methoxycyclization of enynes, [6][7][8] suggesting that this kind of carbene complexes should be incorporated Article Inorganic Chemistry, Vol. 49, No.…”

Carbene Complexes Derived from Metal‐Bound Isocyanides: Recent Advances

“…Notably, most of the complexes described here display luminescent properties [28] . In a related study conducted by Espinet et al [29] , the isocyanide in complexes [AuX(CNPy -2)] (X = Cl, C 6 F 5 , F mes ) were shown to react with H 2 NMe or HNEt 2 to produce the aminocarbene species [AuX{C(NR 1 R 2 )(NHPy -2)}]. The NHPy -2 moiety generated in this reaction gives rise to either intramolecular (for primary amines) or intermolecular (for secondary amines) hydrogen bonds.…”

“…The NHPy -2 moiety generated in this reaction gives rise to either intramolecular (for primary amines) or intermolecular (for secondary amines) hydrogen bonds. Except for the fl uoromesityl derivatives, the carbene complexes display luminescent properties [29] .…”