813-19-4Relevant articles and documents
Reactivity of lanthanide and yttrium hydrides and hydrocarbyls toward organosilicon hydrides and related compounds
Voskoboynikov, Alexander Z.,Parshina, Inna N.,Shestakova, Alia K.,Butin, Kim P.,Beletskaya, Irina P.,KuZ'Mina, Lyudmila G.,Howard, Judith A. K.
, p. 4041 - 4055 (1997)
The reaction of lanthanide and yttrium hydrocarbyls {Cp*2Ln(μ-Me)}2 (Cp* = tBuC5H4 (Cp′), Ln = Y (1), Tb (2), Yb (3), Lu (4); Cp* = Me3SiC5H4 (Cp″), Ln = Lu (5)), one of which, 2, has been characterized by X-ray crystal analysis, with various organosilicon, -germanium, and -tin hydrides (as well as some organoaluminum and -gallium hydrides) in hydrocarbon solution was found to yield the corresponding unsolvated dimeric lanthanide and yttrium hydrides {Cp*2Ln(μ-H)}2 rather than compounds with lanthanide-element (Si, Ge, Sn) bonding. Thus, the reaction involves hydride transfer to Ln rather than the silyl transfer studied earlier for pentamethylcyclopentadienyllanthanide hydrocarbyls. Dimeric compounds Cp*2Ln(μ-H)(μ-Me)LnCp*2 with different bridging ligands were isolated; they are intermediates in this reaction. Dimeric lanthanide and yttrium hydrides catalyze the H/D exchange in silanes. This catalytic reaction is most correctly described by a mechanism involving nucleophilic substitution at the silicon atom. Yttrium and lutetium hydrocarbyls 1 and 4 react with various alkoxysilanes to produce the dimeric alkoxides {Cp′2Ln(μ-OR)}2 or the hydrocarbyl alkoxides Cp′2Ln(μ-Me)(μ-OR)LnCp′2 (R = Me, Et), depending on the reaction conditions. The reaction of 4 with (MeO)4Si provided Cp′2Lu(μ-Me)(μ-OMe)LuCp′2, which has been characterized by X-ray crystal analysis. This compound contains one methyl bridge (Lu-C 2.57(2) and 2.58(2) A?) and nonsymmetrically bonded μ-OMe ligand (Lu-O 2.20(2) and 2.12(2) A?). The reaction of 1 and 4 with Me3SiCl leads to the corresponding dimeric chlorides {Cp′2Ln(μ-Cl)}2 only. Thus, the reaction of lanthanide and yttrium hydrocarbyls with various heterosubstituted organosilanes R3SiX, where X = H, OR, or Cl, is a selective and convenient synthetic method in the chemistry of the group 3 elements. Complexes with Ln(μ-H)(μ-Me)Ln and Ln(μ-H)(μ-Cl)Ln bridging were prepared in high yield by the exchange reactions between the corresponding dimeric compounds {Cp*2Ln(μ-X)}2 (X = H, Me, Cl) in a hydrocarbon solution. The capacities of various bridging fragments to undergo reversible cleavage (dissociation) in the hydrocarbon solution increase in the sequence Ln-O(Me)-Ln ? Ln-Cl-Ln Ln-H-Ln Ln-Me-Ln.
Transformations of organosilanes by Pt(II) complexes with hemilabile P,N-chelating ligands
Schubert, Ulrich,Pfeiffer, Jürgen,St?hr, Frank,Sturmayr, Dietmar,Thompson, Susan
, p. 53 - 58 (2002)
The article reviews the author's own work to enhance the reactivity of Pt(II) complexes towards organosilanes by employing hemilabile chelating ligands R2N-R′-PPh2 (P∩N). Variation of the groups R and R′ allows to influence the react
Spectroscopic studies of tributylstannyl radical. Rates of formation, termination, and abstraction determined by transient absorption spectroscopy
Shaw, Wendy J.,Kandandarachchi, Pramod,Franz, James A.,Autrey, Tom
, p. 2080 - 2086 (2004)
Transient absorption spectroscopy (TAS) was used to measure the rate of formation and the rate of self-termination of the main group metal hydride, tri-n-butyltin hydride (Bu3-SnH). Irradiation of di-tert-butyl peroxide in the presence of Busu
Illuminating Stannylation
Sakamoto, Kyoka,Nagashima, Yuki,Wang, Chao,Miyamoto, Kazunori,Tanaka, Ken,Uchiyama, Masanobu
supporting information, p. 5629 - 5635 (2021/05/04)
We have developed photoboosted stannylation reactions of terminal alkynes (linear-selective hydrostannylation) and fluoroarenes (defluorostannylation), in which the stannyl anion is photoexcited to an excited triplet (T1) stannyl diradical species. This u
A Drastic Effect of TEMPO in Zinc-Catalyzed Stannylation of Terminal Alkynes with Hydrostannanes via Dehydrogenation and Oxidative Dehydrogenation
Kai, Yuichi,Oku, Shinya,Sakurai, Kyoko,Tani, Tomohiro,Tsuchimoto, Teruhisa
supporting information, (2019/08/21)
With a system consisting of a catalytic zinc Lewis acid, pyridine, and TEMPO in a nitrile medium, terminal alkynes coupled with HSnBu3, providing alkynylstannanes with structural diversity. The resulting alkynylstannane, without being isolated, could be directly used for Pd- and Cu-catalyzed transformations to deliver internal alkynes and more intricate tin-atom-containing molecules. Mechanistic studies indicated that TEMPOSnBu3 formed in situ from TEMPO and HSnBu3 works to stannylate the terminal alkyne in collaboration with the zinc catalyst, and that both of dehydrogenation and oxidative dehydrogenation processes are uniquely involved in a single reaction. (Figure presented.).