79271-56-0Relevant articles and documents
Heterolytic activation of H-X (X = H, Si, B, and C) bonds: An experimental and theoretical investigation
Nagaraja,Parameswaran, Pattiyil,Jemmis, Eluvathingal D.,Jagirdar, Balaji R.
, p. 5587 - 5596 (2007)
The highly electrophilic, coordinatively unsaturated, 16-electron [Ru(P(OH)3)(dppe)2][OTf]2 (dppe = Ph 2PCH2CH2PPh2) complex 1 activates the H-H, the Si-H, and the B-H bonds, in H2(g), EtMe2SiH and Et3SiH, and H3B·L (L = PMe3, PPh3), respectively, in a heterolytic fashion. The heterolysis of H2 involves an η2-H2 complex (observable at low temperatures), whereas the computations indicate that those of the Si-H and the B-H bonds proceed through unobserved η1-species. The common ruthenium-containing product in these reactions is trans-[Ru(H)(P(OH) 3)(dppe)2][OTf], 2. The [Ru(P(OH)3)(dppe) 2][OTf]2 complex is unique with regard to activating the H-H, the Si-H, and the B-H bonds in a heterolytic manner. These reactions and the heterolytic activation of the C-H bond in methane by the model complex [Ru(POH)3)-(H2PCH2CH2PH 2)2][CI][OTf], 4, have been investigated using computational methods as well, at the B3LYP/ LANL2DZ level. While the model complex activates the H-H, the Si-H, and the B-H bonds in H2, SiH4, and H3B·L (L = PMe3, PPh 3), respectively, with a low barrier, activation of the C-H bond in CH4 involves a transition state of 57.5 kcal/mol high in energy. The inability of the ruthenium complex to activate CH4 is due to the undue stretching of the C-H bond needed at the transition state, in comparison to the other substrates.
Zinc-catalyzed silylation of terminal alkynes
Rahaim Jr., Ronald J.,Shaw, Jared T.
, p. 2912 - 2915 (2008/09/19)
(Chemical Equation Presented) A rapid and high-yielding silylation of terminal alkynes employing TMSOTf and catalytic quantities of Zn(OTf) 2 has been developed. The reaction works well for a variety of substrates including reactive esters. Fifteen examples with yields of >90% are reported.
Lewis acid mediated Peterson fluoroolefination
Welch, John T.,Gregor, Tamas,Kornilov, Andrei
, p. 171 - 178 (2007/10/03)
Peterson olefination of the alkyl and aryl aldehydes with C,O-bis(triethylsilyl)fluoroketene acetal 1 promoted by titanium tetrachloride and dimethylaluminum chloride was investigated. Desired fluoroolefins were formed with high stereoselectivity and moderate to high yields.