31576-68-8Relevant academic research and scientific papers
14-Electron Rh and Ir silylphosphine complexes and their catalytic activity in alkene functionalization with hydrosilanes
Abeynayake, Niroshani S.,Donnadieu, Bruno,Gorla, Saidulu,Montiel-Palma, Virginia,Mu?oz-Hernández, Miguel A.,Zamora-Moreno, Julio
supporting information, p. 11783 - 11792 (2021/09/06)
Herein we report an experimental and computational study of a family of four coordinated 14-electron complexes of Rh(iii) devoid of agostic interactions. The complexes [X-Rh(κ3(P,Si,Si)PhP(o-C6H4CH2SiiPr2)2], where X = Cl (Rh-1), Br (Rh-2), I (Rh-3), OTf (Rh-4), Cl·GaCl3(Rh-5); derive from a bis(silyl)-o-tolylphosphine with isopropyl substituents on the Si atoms. All five complexes display a sawhorse geometry around Rh and exhibit similar spectroscopic and structural properties. The catalytic activity of these complexes and [Cl-Ir(κ3(P,Si,Si)PhP(o-C6H4CH2SiiPr2)2],Ir-1, in styrene and aliphatic alkene functionalizations with hydrosilanes is disclosed. We show thatRh-1catalyzes effectively the dehydrogenative silylation of styrene with Et3SiH in toluene while it leads to hydrosilylation products in acetonitrile.Rh-1is an excellent catalyst in the sequential isomerization/hydrosilylation of terminal and remote aliphatic alkenes with Et3SiH including hexene isomers, leading efficiently and selectively to the terminal anti-Markonikov hydrosilylation product in all cases. With aliphatic alkenes, no hydrogenation products are observed. Conversely, catalysis of the same hexene isomers byIr-1renders allyl silanes, the tandem isomerization/dehydrogenative silylation products. A mechanistic proposal is made to explain the catalysis with these M(iii) complexes.
Combinatorial Approach to the Catalytic Hydrosilylation of Styrene Derivatives: Catalyst Systems Composed of Organoiron(0) or (II) Precursors and Isocyanides
Sunada, Yusuke,Noda, Daisuke,Soejima, Hiroe,Tsutsumi, Hironori,Nagashima, Hideo
supporting information, p. 2896 - 2906 (2015/06/30)
(COT)2Fe and the open ferrocenes (MPDE)2Fe (MPDE = η5-3-methylpentadienyl) and (DMPDE)2Fe (DMPDE = η5-2,4-dimethylpentadienyl) were found to function as catalyst precursors for the hydrosilylation of alkenes in the presence of auxiliary ligands. Screening trials determined that the optimal catalyst system was composed of (COT)2Fe and adamantyl isocyanide, allowing the selective hydrosilylation of styrene derivatives with trisubstituted hydrosiloxanes and a polydimethylsiloxane bearing Me2SiH moieties as the end groups. Under the appropriate conditions, the dehydrogenative silylation side reaction was completely suppressed, and the reaction TON exceeded 5000. (Chemical Equation Presented).
Hydrosilylation vs. dehydrogenative silylation of styrene catalysed by iron(0) carbonyl complexes with multivinylsilicon ligands - Mechanistic implications
Marciniec, Bogdan,Kownacka, Agnieszka,Kownacki, Ireneusz,Hoffmann, Marcin,Taylor, Richard
, p. 58 - 65 (2015/06/08)
Well-defined iron(0) complexes with multivinylsilicon ligands of the formula [Fe(CO)3L] and {[Fe(CO)3]2L′}, where L = dienes, trienes or vinylfunctional silicones and L′ = tetraenes, are new very active and effective catal
Hydrosilylation Reaction Catalysts and Curable Compositions and Methods for Their Preparation and Use
-
Paragraph 0178; 0183, (2014/10/16)
A composition contains (A) a hydrosilylation reaction catalyst and (B) an aliphatically unsaturated compound having an average, per molecule, of one or more aliphatically unsaturated organic groups capable of undergoing hydrosilylation reaction. The composition is capable of reacting via hydrosilylation reaction to form a reaction product, such as a silane, a gum, a gel, a rubber, or a resin. Ingredient (A) contains an iron-organosilicon ligand complex that can be prepared by reacting an iron carbonyl compound and an organosilicon ligand.
Simple synthesis ofnewmixed isocyanide-nhc-platinum(ii) complexes and their catalytic activity
Hubbert, Christoph,Breunig, Marcus,Carroll, Kristen J.,Rominger, Frank,Hashmi, A. Stephen K.
, p. 469 - 474 (2014/04/03)
Using the new modular and convergent approach to isocyanide-N-hetrocyclic carbene-platinum(II) complexes, eight new compounds have been synthesised. For three of these, detailed structural data could be obtained by X-ray crystal structure analyses. This n
Functionalization of vinyl-substituted linear oligo- and polysiloxanes via ruthenium catalyzed silylative coupling with styrene
Zak, Patrycja,Skrobańska, Monika,Pietraszuk, Cezary,Marciniec, Bogdan
experimental part, p. 1903 - 1906 (2009/10/01)
Efficient silylative coupling of linear vinyl-substituted oligo- and polysiloxanes with styrene in the presence of [RuHCl(CO)(PPh3)3] (1) and particularly [RuHCl(CO)(PCy3)2] (2) combined with copper(I) chloride
