43185-24-6Relevant academic research and scientific papers
Regioselective Hydrosilylation of Olefins Catalyzed by a Molecular Calcium Hydride Cation
Schuhknecht, Danny,Spaniol, Thomas P.,Maron, Laurent,Okuda, Jun
supporting information, p. 310 - 314 (2019/11/26)
Chemo- and regioselectivity are often difficult to control during olefin hydrosilylation catalyzed by d- and f-block metal complexes. The cationic hydride of calcium [CaH]+ stabilized by an NNNN macrocycle was found to catalyze the regioselective hydrosilylation of aliphatic olefins to give anti-Markovnikov products, while aryl-substituted olefins were hydrosilyated with Markovnikov regioselectivity. Ethylene was efficiently hydrosilylated by primary and secondary hydrosilanes to give di- and monoethylated silanes. Aliphatic hydrosilanes were preferred over other commonly employed hydrosilanes: Arylsilanes such as PhSiH3 underwent scrambling reactions promoted by the nucleophilic hydride, while alkoxy- and siloxy-substituted hydrosilanes gave isolable alkoxy and siloxy calcium derivatives.
Selective synthesis of monohydrosilanes by the reactions of organoytterbium iodides with dihydrosilanes
Jin, Wu-Song,Makioka, Yoshikazu,Kitamura, Tsugio,Fujiwara, Yuzo
, p. 955 - 956 (2007/10/03)
Monohydrosilanes can be prepared selectively in high yields from the reaction of various aryl and alkyl iodides with ytterbium metal followed by the reaction with dihydrosilanes.
Silicon-carbon unsaturated compounds. 57. Photolysis of meso- and racemic-1,2-diethyl-1,2-dimethyldiphenyldisilane, direct evidence for a concerted 1,3-silyl shift to ortho-carbon in the phenyl ring
Ohshita, Joji,Niwa, Hiroyuki,Ishikawa, Mitsuo,Yamabe, Tokio,Yoshii, Takao,Nakamura, Kouichi
, p. 6853 - 6859 (2007/10/03)
meso- and racemic-1,2-diethyl-1,2-dimethyldiphenyldisilane (2a) and (2b) were synthesized respectively by hydrogenation of meso- and racemic-1,2-diethynyl-1,2-dimethyldiphenyldisilane in the presence of a IrCl(CO)(PPh3)2 catalyst. Ir
Reactions of primary and secondary silanes with binuclear rhodium complexes. Formation of μ-silylene complexes and P-Si bonds with facile P-C bond cleavage
Wang, Wei-Dong,Eisenberg, Richard
, p. 1833 - 1841 (2007/10/02)
A series of bis(μ-SiRH) complexes Rh2(μ-SiRH)2(CO)2(OpEm)2 (E = P: 3a, R = Ph; 3b, R = Et; 3c, R = n-C6H13; and E = As: 6a, R = Ph; 6b, R = Et; 6c, R = n-C6H13) has been synthesized from the reaction of the corresponding primary silane RSiH3 and Rh2(μ-H)2(CO)2(dpEm)2 (1, E = P; 4, E = As). The bis μ-SiRH complexes 3 and 6 are characterized by 1H and 31P{1H} NMR and IR spectroscopies and for the Et and Ph derivatives, 3b and 3a, respectively, by X-ray crystallography. Crystallographic data for 3b: C2/c; a = 24.184 (5) A?, b = 9.948 (3) A?, c = 24.059 (5) A?; β = 114.49 (2)°; Z = 4; dcalcd = 1.45 g/cm3; R = 0.034, Rw = 0.045. The structure determination of 3b shows it to be a "cradle-like" structure with a Rh-Rh bond of 2.814 (1) A? and bridging SiEtH ligands. Each Rh center posesses an approximately square pyramidal coordination geometry ignoring the stereochemical influence of the Rh-Rh bond. In the reaction of 1 with RSiH3, an intermediate has been identified as Rh2(μ-SiRH)(H)2(CO)2(dppm)2 (2a, R = Ph; 2b, R = Et; 2c, R = n-C6H13) on the basis of spectroscopic data. This intermediate is fluxional with exchange occurring between Si-H and Rh-H protons, presumably by facile reductive elimination/oxidative addition of Si-H bonds to the Rh centers. For the dpam system 4, different intermediates of the type Rh2(μ-SiRH)(SiRH2)(H)3(CO) 2(dpam)2 (5a, R = Ph; 5b, R = Et; 5c, R = n-C6H13) are observed in the reaction with RSiH3. Secondary silanes RR′SiH2 react with 1 to produce initially the μ-SiRR′ dihydride intermediates Rh2(μ-SiRR′)(H)2(CO)2(dppm) 2 (9a, R = R′ = Me; %, R = R′ = Et; 9c, R = Me, R′ = Ph) but ultimately give a new type of complex in which P-C cleavage and P-Si bond formation have occurred. These complexes are of the formula Rh2(μ-H)(CO)2(dppm)(Ph2PCH 2PPhSiRR′) (10a, R = R′ = Me; 10b, R = R′ = Et; 10c, R = Me, R′ = Ph) and have been characterized by 1H and 31P{1H} NMR and IR spectroscopies, and for 10b by X-ray crystallography. X-ray data for 10b: P21; a = 11.387 (2) A?, b = 18.959 (3) A?, c = 13.354 (2) A?; β = 112.50 (1)°; Z = 2; dcalcd = 1.30 g/cm3; R = 0.029, Rw = 0.041. In a related reaction, the tricarbonyl complex Rh2(CO)3(dppm)2 (7) reacts with RSiH3 leading initially to the formation of 2 followed by conversion to the μ-CO complex Rh2(μ-SiRH)(μ-CO)(CO)2(dppm)2 (8) which can also form by placing a solution of 2 under CO.
METHYLPHENYLTRIPHENYLGERMYLSILANES FONCTIONNELS OPTIQUEMENT ACTIFS. II. REACTIONS DE CLIVAGE DE LA LIAISON Si-Ge
Corriu, R. J. P.,Ould-Kada, S.,Lanneau, G. F.
, p. 39 - 50 (2007/10/02)
The cleavage of a silicon-germanium bond in the presence of organometallics has been studied on the optically active compounds MePh(X)SiGePh3 (X=H, OMe).Depending on the nature of the nucleophile, we obtained mixed products, corresponding to the formation of Ph3Ge-, transient radical-anions, or catalytic reactions.
