A Bis(ortho-amine)aryl−Gold(I) Compound as an Efficient, Nontoxic, Arylating Reagent

Abstract

A novel strategy for the synthesis of bis(ortho-amine)chelated monoanionic bisaminoaryl−metal complexes is presented. This method constitutes the exchange of a monoanionic, NCN-pincer ligand (NCN = [C6H3(CH2NMe2)2-2,6]-) between a stable arylgold(I) phosphine, [Au(η1-C-NCN)(PPh3)] (2), and a transition metal halide. This transmetalation results in the quantitative formation of [M(NCN)] organometallic compounds (M = AuIII, NiII, PdII, PtII, TiIV, and FeIII) and [AuCl(PPh3)] as the only coproduct that can be recovered.

X-Ray and NMR Study of the Structural Features of SCS-Pincer Metal Complexes of the Group 10 Triad

“…All reactions were performed under a dry nitrogen atmosphere by standard Schlenk techniques. Solvents were carefully dried and distilled from sodium benzophenone (pentane, hexane, toluene, C 6 [C 6 H 2 (CH 2 SMe) 2 -2,6-Br-1] (2). Solid 1 (1.0 g, 2.92 mmol) was dissolved in THF (100 mL) and NaSMe (0.97 g, 13.8 mmol) was added in one portion.…”

Gold trifft Palladium für Kreuzkupplungen

“…[3,4] Bis vor kurzem konnten nur symmetrische Moleküle durch die oxidative Dimerisierung von Gold(III)-Intermediaten hergestellt werden, mittlerweile aber haben Zhang et al über eine eindrucksvolle oxidative Kreuzkupplung mit Selectfluor als Reoxidationsreagens berichtet. [5] Unserer Meinung nach gibt es eine weitere Möglichkeit, um die Anwendungsbreite der homogenen Gold-Chemie zu erweitern: die Transmetallierung einer in situ generierten Organogold-Spezies A auf andere Übergangsmetalle wie die Palladium-Spezies B (Schema 1 [6] Hier stellen wir eine Studie des Gold/Palladium-Systems vor, bei der stöchiometrische Mengen an Organogold-Verbindungen und katalytische Mengen an Palladium-Komplexen für Kreuzkupplungen eingesetzt werden. Unser erster Versuch zur Kreuzkupplung von Organogold-Zwischenstufen begann mit einem Test der Palladium-Katalysatoren 1-7 (Abbildung 1) [7] in der Modellreaktion von Iodbenzol mit…”

Reactivity of intramolecularly coordinated aluminum compounds to R3EOH (E = Sn, Si). Remarkable migration of N,C,N and O,C,O pincer ligands

“…Calc. for C 18 ), 120.34 (Ar-C3,5), 127.28 (Ar-C4), 143.85 (Ar-C2,6), (Ar-C1) not found. 27 Al NMR (C 6 D 6 ): 157.7 (m 1/2 = 7.4 kHz).…”

“…Several similar reactions accompanied by migration of N,C,N chelating ligand ð2; 6-ðMe 2 NCH 2 Þ 2 C 6 H À 3 Þ were discovered by van Koten, but these examples were restricted for migration between two transition metals, where the 2,6-(Me 2 NCH 2 ) 2 -C 6 H 3 AuPPh 3 acted as arylating agent for other metals such as Ni, Pd, Pt, Fe, etc. [18], or for reaction of organotin or organosilicon precursors yielding organopalladium derivatives [19].…”