3439-38-1Relevant articles and documents
Ga+-catalyzed hydrosilylation? about the surprising system Ga+/HSiR3/olefin, proof of oxidation with subvalent Ga+and silylium catalysis with perfluoroalkoxyaluminate anions
Barthélemy, Antoine,Glootz, Kim,Hanske, Annaleah,Krossing, Ingo,Scherer, Harald
, p. 439 - 453 (2022/01/22)
Already 1 mol% of subvalent [Ga(PhF)2]+[pf]- ([pf]- = [Al(ORF)4]-, RF = C(CF3)3) initiates the hydrosilylation of olefinic double bonds under mild conditions. Reactions with HSiMe3 and HSiEt3 as substrates efficiently yield anti-Markovnikov and anti-addit
Silylpalladium Cations Enable the Oxidative Addition of C(sp3)-O Bonds
Wierschen, Andreas L.,Romano, Neyen,Lee, Stephen J.,Gagné, Michel R.
supporting information, p. 16024 - 16032 (2019/11/11)
The synthesis and characterization of the room-temperature and solution-stable silylpalladium cations (PCy3)2Pd-SiR3+(C6F5)4B- (SiR3 = SiMe2Et, SiHEt2) and (Xantphos)Pd-SiR3+(BArf4) (SiR3 = SiMe2Et, SiHEt2; Xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; BArf4 = (3,5-(CF3)2C6H3)4B-) are reported. Spectroscopic and ligand addition experiments suggest that silylpalladium complexes of the type (PCy3)2Pd-SiR3+ are three-coordinate and T-shaped. Addition of dialkyl ethers to both the PCy3 and Xantphos-based silylpalladium cations resulted in the cleavage of C(sp3)-O bonds and the generation of cationic Pd-alkyl complexes. Mechanistically enabling is the ability of silylpalladium cations to behave as sources of both electrophilic silylium ions and nucleophilic LnPd(0).
Elongated Gilman cuprates: The key to different reactivities of cyano- and iodocuprates
Neumeier, Maria,Gschwind, Ruth M.
, p. 5765 - 5772 (2014/05/06)
In the past the long-standing and very controversial discussion about a special reactivity of cyano- versus iodocuprates concentrated on the existence of higher-order cuprate structures. Later on numerous structural investigations proved the structural equivalence of iodo and cyano Gilman cuprates and their subsequential intermediates. For dimethylcuprates similar reactivities were also shown. However, the reports about higher reactivities of cyanocuprates survived obstinately in many synthetic working groups. In this study we present an alternative structural difference between cyano- and iodocuprates, which is in agreement with the results of both sides. The key is the potential incorporation of alkyl copper in iodo but not in cyano Gilman cuprates during the reaction. In the example of cuprates with a highly soluble substituent (R = Me 3SiCH2) we show that in the case of iodocuprates during the reaction several copper-rich complexes are formed, which consume additional iodocuprate and provide lower reactivities. To confirm this, a variety of highly soluble copper-rich complexes were synthesized, and their molecular formulas, the position of the equilibriums, their monomers and their aggregation trends were investigated by NMR spectroscopic methods revealing extended iodo Gilman cuprates. In addition, the effect of these copper-rich complexes on the yields of cross-coupling reactions with an alkyl halide was tested, resulting in reduced yields for iodocuprates. Thus, this study gives an explanation for the thus far confusing results of both similar and different reactivities of cyano- and iodocuprates. In the case of small substituents the produced alkyl copper precipitates and similar reactivities are observed. However, iodocuprates with large substituents are able to incorporate alkyl copper units. The resulting copper-rich species have less polarized alkyl groups, i.e. gradually reduced reactivities.
