Reactions of iridium bis(phosphinite) pincer complexes with protic acids

Iridium pincer complexes [C₆H₃-2,6-(OPBu^t ₂)₂]Ir(H)Cl (10) and [4-EtOOCC₆H₂-2,6-(OPBu^t ₂)₂]Ir(H)Cl (11) react with protic acids undergoing metallation of one of the tert-butyl groups to form double cyclometallated products [4-R-C₆H₂-2-(OPBu^t ₂)-6-(OP(Bu^t)CMe₂CH₂)]IrCl (12, R = H; 13, R = COOEt), which are stable in air. Complex 12 reacts with CO and Bu^tNC giving the corresponding 18-electron complexes [C₆H₃-2-(OP-Bu^t ₂)-6-(OP(Bu^t)CMe₂CH₂)]Ir(L)Cl (14, L = CO; 15, L = CNBu^t). The structure of compound 14 was established by X-ray diffraction analysis.     

Palladium-catalyzed allylic substitution assisted by 1,3,2-diazaphospholidine derivatives of (<Emphasis Type="Italic">R,R</Emphasis>)-<Emphasis Type="Italic">N</Emphasis>-naphthyltartarimide

P,P-Bidentate diamidophosphite ligands containing the (3R,4R)-3,4-dioxy-1-(1-naphthyl)pyrrolidine-2,5-dione framework and 1,3,2-diazaphospholidine rings with the stereogenic P atoms were obtained. The use of these ligands provides up to 85% ee in Pd-catalyzed asymmetric amination of (E)-1,3-diphenylallyl acetate and up to 95% ee in its asymmetric alkylation with dimethyl malonate.     

Carboranyl phosphites: the electronic effect in the Suzuki- Miyaura reaction

Isomeric carborane-containing phosphite ligands possessing different electronic properties have been synthesized. Their use in the Pd-catalyzed Suzuki-Miyaura reaction involving activated aryl bromides showed that phosphite with 9-o-carborane substituent has proved more efficient, with carboranyl phosphite having 1-m- carborane fragment being more efficient in the reactions with nonactivated aryl bromides.     

The first one-pot ‘alkane-like’ reactions of carbonyl-containing adamantanes

A novel ‘alkane-like’ methodology for the direct and very simple one-pot functionalization of amides and an ester of 1-adamantanecarboxylic acid provides access to new and synthetically challenging 1,3-dicarbonyl-containing adamantanoid compounds with the same or different functional groups.     

Synthesis of the first unsymmetrical 34-electron cationic cobalt-nickel triple-decker complex with a central cyclopentadienyl ligand [(η-C6Me6)Co(μ-η:η-C5H5)Ni(η-C5H5)]PF6

The first unsymmetrical 34-electron cationic cobalt-nickel triple-decker complex with a central cyclopentadienyl ligand [(η-C₆Me₆)Co(μ-η:η-C₅H₅)Ni(η-C₅)PF₆ was prepared by the reaction of [(η-C₆Me₆)₂Co]PF₆ with nickelocene. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 798–799, April, 1999.     

Polymeric multideck sandwich complex of trimeric perfluoro-o-phenylenemercury with bromide anion

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1466–1467, June, 1991.