A Structural Probe for Organogold(I) Rings and [2]Catenanes

Abstract

The digold(I) diacetylides [4-RC 6 H 9 (4-C 6 H 4 OCH 2 CtCAu) 2 ], which contain a cyclohexylidene hinge group 4-RC 6 H 9 with R ) H or t-Bu, react with diphosphine ligands Ph 2 PZPPh 2 to give the corresponding macrocycles orBu, the bulky tert-butyl group locks the cyclohexane ring conformation and so provides a good NMR spectroscopic probe of the structure. The organogold(I) [2]catenane complexes are chiral when R ) t-Bu, and the complex with Z ) (CH 2 ) 4 gives an equilibrium in solution between ring, double-ring, and [2]catenane. When R ) H and Z ) (CH 2 ) 3 , the variabletemperature NMR spectra give new insight into the fluxionality in the [2]catenane complex, and when R ) H and Z ) (CH 2 ) 4 , it is shown that the complex exists in solution as the ring structure, although it crystallizes as a doubly braided [2]catenane.

Gold–Gold Interactions

“…The crystal structures of ring and [2]catenates have been described whereas crystal structures of doubly braided [2]catenates are much less frequent. In these structures gold-gold interactions may combine with hydrogen bonds and p-p interactions [303][304][305][306].…”

Photoactive building blocks for coordination complexes: Gilding 2,2′:6′,2″-terpyridine

“…Gold(I) alkynyl complexes [1,2] containing gold atoms in linear coordination environments are popular building blocks for polymeric and macrocyclic organometallic assemblies [3][4][5][6][7][8][9][10][11][12]. The luminescent properties of gold(I) species [13,14] and the ease of synthesis of gold(I) alkynyls make them attractive candidates for derivatization of other metal-binding domains such as pyridine [15][16][17][18][19], 2,2'-bipyridine (bpy) [16,20,21] and 2,2':6',2"-terpyridine (tpy) [21,22].…”

Study of the Effect of the Phosphane Bridging Chain Nature on the Structural and Photophysical Properties of a Series of Gold(I) Ethynylpyridine Complexes

“…[6][7][8][9][10][11][12] Moreover, the low steric congestion about the linear gold(I) centre and the ability of gold(I) to form attractive Au···Au interactions have made alkynyl gold(I) compounds attractive candidates for the synthesis of a wide variety of supramolecular structures [13] as polymers, [14][15][16][17] macrocycles [18][19][20] or catenanes. [21][22][23][24] One rather unexplored way of building up metallamacrocycles containing these subunits is to utilise alkynyl ligands with a second binding site. In this context, the introduction of ethynylpyridine fragments into alkynyl gold(I) complexes allows the obtention of potentially useful building blocks towards the synthesis of heterometallic macrocycles or polymers.…”