(Isocyanoaryl)acetylides as bridging ligands in rigid-rod polymers: mononuclear and oligonuclear gold(I) complexes

Abstract

The new ethynylaryl isocyanide ligands 4-C=NCeH4C=CH (la) and 4-C=N-3-MeCeH3-C=CH (lb) have been prepared. They react with [AuCl(SMe2)] and with [(AuC=C-f-Bu)x] to give the isocyanide complexes [ClAu(4-C=NArC=CH) j (2a, Ar = CeH4; 2b, Ar = 3-MeC3H3) and [í-BuO^CAu(4-C=NArC^CH)] (6a, Ar = C3H4; 6b, Ar = 3-MeCeH3), respectively. The complex [í-BuC=CAuC=NXy] (Xy = 2,6-Me2CeH3) reacts with the acidic alkyne 4-N02-C3H4C=CH to give . A similar reaction uses the more acidic alkyne in 6 to displace -BuC^CH from 6 and so give the linear rigid-rod oligomers [í-BuC^C(AuC=NArC=C-)xH] (7a, Ar = C6H4; 7b, Ar = S-MeCeHg). The complexes 2a and 6b have been characterized by X-ray structure determinations (2a, monoclinic, P2Jm, a =

Synthesis and Uses of Organogold Compounds

“…Tetraarylaurate(III) complexes containing polyhalophenyl ligands 11,12 are best prepared by further arylation of triarylhaloaurates(III) with Ag(C 6 F 5 ) (equation 85 …”

Effect of the organic fragment on the mesogenic properties of a series of organogold(I) isocyanide complexes. X-ray crystal structure of [Au(CCC5H4N)(CNC6H4O(O)CC6H4OC10H21)]

“…[AuCl(CNC 6 H 4 -O(O)CC 6 H 4 OC 10 H 21 10 H 21 -p in a CH 2 Cl 2 solution at room temperature. Compounds 2b, 3b and 4b were synthesized in good yields using the reactions outlined in Scheme 1, following a well-known strategy [5]. Firstly, the free acetylenes were reacted with [AuCl(tht)] (tht = tetrahydrothiophene) in the presence of NaOAc as base to give the insoluble [Au(C"CR 0 )] n derivatives (2a, 3a and 4a).…”

“…On the other hand, a number of gold acetylide compounds have been shown to be excellent precursors for species showing liquid crystal behaviour because of the linear shape of the MAC"CAR moiety and the lack of b-hydrogen atoms in the MAC"C bond [4]. Looking at this second point, it is worth noting that linear gold complexes containing substituted acetylide groups may easily incorporate, through well established methods [5], ligands, such as isonitriles, that can give to the resulting species liquid crystalline properties. Less known for this purpose are the gold compounds containing fluorinated aryl rings [6], which interestingly, render more thermally stable 0022 compounds.…”

Metall‐Alkinyl‐σ‐Komplexe: Synthesen und Materialien

“…[232] Zweikernige Au I -Diarylalkinylkomplexe [Au-CC-Ar-CC-Au] n (Ar = Arenspacer) sind aus [AuCl(SMe 2 )] und dem entsprechenden Aryldialkin zugänglich. [233,234] Die Komplexe können mit Aryldiisocyaniden in Polymere vom Typ [Ar-CC-Ar-CC-Au-CN-R-NC] n überführt werden, [233][234][235] allerdings verhindern Löslichkeitsprobleme [235] oder intermolekulare Au···Au-Wechselwirkungen. [233] Die Au···Au-Wechselwirkungen, die von relativistischen London-Kräften herrühren, haben vermutlich die Stärke von Wasserstoffbrücken (ca.…”