104834-20-0Relevant academic research and scientific papers
Trans additions of silanes to 1-alkynes catalyzed by ruthenium complexes: Role of in situ formed polynuclear aggregates
Martín, Marta,Sola, Eduardo,Lahoz, Fernando J.,Oro, Luis A.
, p. 4027 - 4029 (2002)
Role of in situ formed polynuclear aggregates in trans addition of silanes to 1-alkynes catalyzed by ruthenium complexes was investigated. Alkenyl ligands were formed by insertion of 1-alkynes into bridging hydrides. The unusual strereoselectivity of this
Ruthenium-catalyzed hydrosilylation of terminal alkynes: Stereodivergent synthesis of (E)- and (Z)-alkenylsilanes
Katayama, Hiroyuki,Taniguchi, Ken,Kobayashi, Masayuki,Sagawa, Takashi,Minami, Tatsuya,Ozawa, Fumiyuki
, p. 192 - 200 (2007/10/03)
Stereodivergent hydrosilylation of terminal alkynes (RC≡CH; R = Ph, p-tolyl, Cy, n-hexyl) with hydrosilanes (HSiMe2Ar; Ar=Ph, 3,5-(CF3)2C6H3, 4-CF3C6H4, 4-MeOC6H4) has been examined using ruthenium catalysts. (E)-selective reactions giving (E)-RCH=CHSiMe2Ar proceed in over 99% selectivity in the presence of a catalytic amount of RuHCl(CO)(PPh3)3. On the other hand, (Z)-selective reactions are successfully conducted in 91-99% selectivity by using Ru(SiMe2Ph)Cl(CO)(PPri3)2 as the catalyst. All reactions readily proceed at room temperature in high yields. (E)- and (Z)-styrylsilanes having a SiMe2 [C6H3-3,5-(CF3)2] group serve as good cross-coupling reagents with p-iodotoluene in the presence of tetrabutylammonium fluoride and [Pd(η3-allyl) Cl]2 catalyst.
Insertion reactions of the 16-electron complexes MHCl(CO)(P-i-Pr3)2 (M = Ru, Os) with alkynes. The X-ray crystal structure of Os((E)-CH=CHPh)Cl(CO)(P-i-Pr3)2
Werner, Helmut,Esteruelas, Miguel A.,Otto, Heiko
, p. 2295 - 2299 (2008/10/08)
The carbonyl hydrido complexes MHCl(CO)(P-i-Pr3)2 (M = Ru, Os) react with alkynes HC≡CR (R = Ph, H) by insertion to give the five-coordinate vinylmetal compounds M(CH=CHR)Cl(CO)(P-i-Pr3)2 (3-6) in nearly quantitative yields. Addition of CO or displacement of the chloride ligand in 3-6 by acetate or acetylacetonate produces the six-coordinate complexes M(CH=CHR)Cl(CO)2(P-i-Pr3)2 (R = Ph; 7, 8), M(CH=CHR)(η2-O2CMe)(CO)(P-i-Pr3) 2 (R = Ph; 9, 10) and M(CH=CHR)(η2-acac)(CO)(P-i-Pr3)2 (R = H, Ph; 11-14), respectively. Treatment of RuHCl(CO)(P-i-Pr3)2 with HC≡CPh and KOH in methanol leads to a mixture of Ru(C≡CPh)2(CO)(P-i-Pr3)2 (15) and Ru(C≡CPh)(CH≡CHPh)(CO)(P-i-Pr3)2 (16), the latter of which reacts with CO to form the octahedral compound Ru(C≡Ph)(CH=CHPh)(CO)2(P-i-Pr3)2 (17). The molecular structure of Os(CH=CHPh)Cl(CO)(P-i-Pr3)2 (4) has been determined by X-ray investigation. 4 crystallizes in the space group P21/n with a = 16.437 (5) A?, b = 10.980 (4) A?, c = 17.086 (4) A?, and β = 105.56 (2)°. The osmium atom has a nearly perfect square-pyramidal coordination with the vinyl ligand in the apical position and the two phosphines trans to each other in the base of the pyramid. With regard to the stereochemistry at the vinyl C=C bond, only the E isomer is formed. A stereo ORTEP diagram illustrates that the metal atom, although coordinatively unsaturated, nevertheless is well shielded at the sixth position of the (uncompleted) octahedron by four of the 12 methyl groups of the phosphine ligands. IR as well as 1H, 13C, and 31P NMR data of the complexes 3-17 are reported.
