2611-02-1Relevant articles and documents
Synthesis of Highly Fluorinated Arene Complexes of [Rh(Chelating Phosphine)]+ Cations, and their use in Synthesis and Catalysis
McKay, Alasdair I.,Barwick-Silk, James,Savage, Max,Willis, Michael C.,Weller, Andrew S.
, p. 2883 - 2889 (2020/02/20)
The synthesis of rhodium complexes with weakly binding highly fluorinated benzene ligands is described: 1,2,3-F3C6H3, 1,2,3,4-F4C6H2 and 1,2,3,4,5-F5C6H are shown to bind with cationic [Rh(Cy2P(CH2)xPCy2)]+ fragments (x=1, 2). Their structures and reactivity with alkenes, and use in catalysis for promoting the Tishchenko reaction of a simple aldehyde, are demonstrated. Key to the synthesis of these complexes is the highly concentrated reaction conditions and use of the [Al{OC(CF3)3}4]? anion.
Organoaluminum cations for carbonyl activation
Kannan, Ramkumar,Chambenahalli, Raju,Kumar, Sandeep,Krishna, Athul,Andrews, Alex P.,Jemmis, Eluvathingal D.,Venugopal, Ajay
supporting information, p. 14629 - 14632 (2019/12/11)
In search of stable, yet reactive aluminum Lewis acids, we have isolated an organoaluminum cation, [(Me2NC6H4)2Al(C4H8O)2]+, coordinated with two labile tetrahydrofuran ligands. Its catalytic performance in aldehyde dimerization reveals turn-over frequencies reaching up to 6000 h-1, exceeding that of the reported main group catalysts. The cation is further demonstrated to catalyze hydroelementation of ketones. Mechanistic investigations reveal that aldehyde dimerization and ketone hydrosilylation occur through carbonyl activation.
Base-Free and Acceptorless Dehydrogenation of Alcohols Catalyzed by an Iridium Complex Stabilized by a N, N, N-Osmaligand
Alabau, Roberto G.,Esteruelas, Miguel A.,Martínez, Antonio,Oliván, Montserrat,O?ate, Enrique
, p. 2732 - 2740 (2018/09/10)
The preparation of a N,N,N-osmaligand, its coordination to iridium to afford an efficient catalyst precursor, and the catalytic activity of the latter in dehydrogenation reactions of hydrogen carriers based on alcohols are reported. Complex OsH2Cl2(PiPr3)2 (1) reacts with 3-(2-pyridyl)pyrazol to give the osmium(II) complex 2H, which contains an acidic hydrogen atom. Deprotonation of the latter by the bridging methoxy groups of the dimer [Ir(μ-OMe)(n4-COD)]2 (COD = 1,5-cyclooctadiene) leads to Ir(2)( n 4-COD) (3), where osmaligand 2 has a free-nitrogen atom. Iridium complex 3 catalyzes the dehydrogenation of secondary and primary alcohols to ketones and aldehydes or esters, respectively, and the dehydrogenation of diols to lactones. Cyclooctatriene is detected during the catalysis by GC-MS, suggesting that the true catalyst of the reactions is a dihydride IrH2(2)-species with osmaligand 2 acting as N,N,N-pincer. The presence of a phenyl group in the substrates favors the catalytic processes. The dehydrogenative homocoupling of primary alcohols to esters appears to take place via the transitory formation of hemiacetals.
