60898-04-6Relevant articles and documents
Gold Difluorocarbenoid Complexes: Spectroscopic and Chemical Profiling
Tskhovrebov, Alexander G.,Lingnau, Julia B.,Fürstner, Alois
supporting information, p. 8834 - 8838 (2019/05/28)
Gold carbenes of the general type [LAu=CR2]+ are sufficiently long-lived for spectroscopic inspection only if the substituents compensate for the largely missing stabilization of the carbene center by the [LAu]+ fragment. π-Donation by two fluorine substituents (R=F) is insufficient; rather, difluorocarbene complexes are so deprived in electron density that they sequester even “weakly coordinating” anions such as triflate or triflimide. This particular bonding situation translates into unmistakable carbenium ion chemistry upon reaction with stilbene as a model substrate.
Synthesis of Au(I) trifluoromethyl complexes. Oxidation to Au(III) and reductive elimination of halotrifluoromethanes
Blaya, Mara,Bautista, Delia,Gil-Rubio, Juan,Vicente, Jos
, p. 6358 - 6368 (2015/02/19)
Au(I) trifluoromethyl complexes [Au(CF3)L] (L = N-heterocyclic carbene (NHC), isonitrile, phosphine, P(OMe)3) and [Au2(CF3)2(-dppe)] are prepared by reaction of [Au(X)L] (X = Cl, I) or [Au2Cl2(-dppe)], respectively, with AgF and Me3SiCF3. The analogous reaction of PPN[Au(C6F5)Cl] (PPN+ = [Ph3PNPPh3]+) gives a mixture of complexes of the type PPN[Au(CF3)x(C6F5)2-x] (x = 0, 1, 2). Single crystals of the new complex PPN[Au(CF3)(C6F5)] are obtained by liquid diffusion from this mixture, and its crystal structure was determined by X-ray diffraction. Acyclic diaminocarbene complexes [Au(CF3){C(NEt2)(NHR)}] (R = tBu, 2,6-dimethylphenyl) are obtained by reaction of [Au(CF3)(CNR)] with NHEt2. Oxidation of the NHC complex [Au(CF3)(IPr)] (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) with PhICl2, Br2, I2 or ICl affords [Au(CF3)(X)(Y)(IPr)] (X = Y = Cl, Br I; X = Cl, Y = I). The dicloro, dibromo, and chloro(iodo) complexes are stable in solution in the dark. In contrast, the diiodo complex is unstable and decomposes to [AuI(IPr)] and ICF3. Under photoirradiation, complexes [Au(CF3)(X)(Y)(IPr)] undergo reductive elimination to give YCF3 and [AuX(IPr)] (X = Y = Cl, Br; X = Cl, Y = I).
C-Si bond cleavage of trihalomethyltrimethylsilane by alkoxo- and aryloxogold or -copper complexes
Usui, Yoko,Noma, Junko,Hirano, Masafumi,Komiya, Sanshiro
, p. 151 - 154 (2008/10/08)
The C-Si bond cleavage of trihalomethyltrimethylsilane Me3SiCX3 (X = F, Cl) proceeds smoothly by alkoxo- and aryloxogold(I or III) or -copper(I) complexes Au(OR)L (OR = OCH(CF3)2, OPh), L =PCy3, PPhs
