14355-62-5Relevant academic research and scientific papers
Selective hydrosilylation of styrene using an in situ formed platinum(1,3-dimesityl-dihydroimidazol-2-ylidene) catalyst
Sprengers, Jeroen W.,Mars, Maayke J.,Duin, Marcel A.,Cavell, Kingsley J.,Elsevier, Cornelis J.
, p. 149 - 152 (2003)
A highly active and selective in situ formed platinum(N-heterocyclic carbene) catalyst for the hydrosilylation of styrene with triethylsilane is described, which unlike all other known hydrosilylation catalysts, selectively yields hydrosilylation products, but (almost) no dehydrogenative silylation products.
Photoactivated telomerization of 1,1,3,3-tetramethyl-1,3-disilacyclobutane with hydrosilanes by Pt(acac)2 and its competition with hydrosilylation addition
Wu, Xiaosong,Malpert, John H.,Zang, Hongmei,Neckers, Douglas C.
, p. 8309 - 8312 (1999)
Telomerization of 1,1,3,3-tetramethyl-1,3-disilacyclobutane with hydrosilanes is facilitated by UV irradiation in the presence of Pt(acac)2. When olefin is also present, photoactivated hydrosilylation competes with telomerization. The dependence of product distribution on the reactivity of the hydrosilanes and the olefins was studied.
Hydrosilylation of olefins catalyzed by well-Defined cationic aluminum complexes: Lewis acid versus insertion mechanisms
Jakobsson, Kayla,Chu, Terry,Nikonov, Georgii I.
, p. 7350 - 7356 (2016)
The cationic aluminum complex [NacNacAlH]+ (2; NacNac = CH{C(Me)N(2,6-Pri2C6H3)}2) can be easily generated from NacNacAlH2 by hydride abstraction and functions as a catalyst for the hydrosilylation of olefins and alkynes. Mechanistic studies suggest that, although olefin insertion into the Al?H bond is very facile, the catalysis does not proceed by an insertion/metathesis mechanism but likely by Lewis acid activation. Stoichiometric reactions of 2 with alkynes furnished unexpected products of CC addition across the NacNacAl moiety to give tripodal aluminum cations, which are also potent catalysts for the hydrosilylation of alkynes.
Variable coordination of a chiral diphosphine containing an amidinium/NHC group within its backbone: μ-P,P′, κ2-P,P′ and κ3-P,C,P′ coordination modes
Newman, Paul D.,Cavell, Kingsley J.,Kariuki, Benson M.
, p. 12395 - 12407 (2012)
A diphosphine ligand (1·HPF6), which is a potential precursor to a PCNHCP pincer, with a backbone containing two phenylene groups and a central bicyclic 4-aza-2-azoniabicyclo[3.2.1]oct-2-ene unit has been synthesised and coordinated to Pd(ii) and Pt(ii) to give trans-[M(κ2-P,P′-1·H)Cl2]PF 6 where M = Pd (2) or Pt (3a). Single-crystal structure determinations of 2 and 3a show the complexes to be isostructural with the diphosphine coordinated in a trans-spanning fashion and the amidinium unit being protonated and non-coordinated. 2 and 3a react with CH3I to give the dimers trans-[Pd2(μ-1·H)2I4](PF 6)2, 6, and trans-[Pt2(μ-1·H) 2I4](PF6)2, 7, as the major products. This bridging mode of coordination of [1·H]+ is also seen in trans-[Rh2(μ-1·H)(1,5-COD)2Cl 2]PF6, 4, and [Pt2(μ-κ2- 1·H)(dvdms)]PF6, 5. Upon treatment with KOtBu complexes 2 and 3a undergo deprotonation at the amidinium carbon to give trans-[M(κ3-P,C,P′-1)Cl]PF6 where M = Pd (8), and Pt (9). The related trans-[Rh(κ3-P,C,P′-1)(CO)] PF6 (10) is prepared directly from 1·HPF6 and Rh(acac)(CO)2: this and the palladium and platinum complexes 8 and 9 are isolated as isomeric mixtures as a consequence of a conformational isomerism. In situ deprotonation of 1·HPF6 followed by addition of Ag(CF3SO3) gave SAg- [Ag(κ3-P,C,P′-1)(CF3SO3)], 11. Some preliminary studies of the reactivity of 2 and 8 in Suzuki-type reactions are reported and the Pt(0) system has been shown to be an active hydrosilylation catalyst.
Rhodium-catalyzed anti-Markovnikov hydrosilylation of alkenes
Liu, Wei,Lu, Wenkui,Wu, Xiaoyu,Yang, Liqun,Zhang, Zhaoguo
supporting information, (2022/02/01)
Rh-catalyzed anti-Markovnikov hydrosilylation of terminal alkenes and tertiary silanes using readily-available PPh3 as the ligand was reported. This method facilitated the effective synthesis of alkylsilanes with a wide substrate scope and high
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.
An air-stable, Zn2+-based catalyst for hydrosilylation of alkenes and alkynes
Dobrovetsky, Roman,Groutchik, Kristina,Jaiswal, Kuldeep
supporting information, p. 5544 - 5550 (2021/07/02)
Hydrosilylation of C-C double and C-C triple bonds is one of the most widely used processes in organosilicon chemistry, mostly catalyzed by Pt-based complexes. We report here the synthesis of an air-stable dicationic Zn2+-based complex in a hem
Manganese-catalysed divergent silylation of alkenes
Dong, Jie,Yuan, Xiang-Ai,Yan, Zhongfei,Mu, Liying,Ma, Junyang,Zhu, Chengjian,Xie, Jin
, p. 182 - 190 (2020/12/17)
Transition-metal-catalysed, redox-neutral dehydrosilylation of alkenes is a long-standing challenge in organic synthesis, with current methods suffering from low selectivity and narrow scope. In this study, we report a general and simple method for the manganese-catalysed dehydrosilylation and hydrosilylation of alkenes, with Mn2(CO)10 as a catalyst precursor, by using a ligand-tuned metalloradical reactivity strategy. This enables versatility and controllable selectivity with a 1:1 ratio of alkenes and silanes, and the synthetic robustness and practicality of this method are demonstrated using complex alkenes and light olefins. The selectivity of the reaction has been studied using density functional theory calculations, showing the use of an iPrPNP ligand to favour dehydrosilylation, while a JackiePhos ligand favours hydrosilylation. The reaction is redox-neutral and atom-economical, exhibits a broad substrate scope and excellent functional group tolerance, and is suitable for various synthetic applications on a gram scale. [Figure not available: see fulltext.].
Nickel(ii)-catalyzed reductive silylation of alkenyl methyl ethers for the synthesis of alkyl silanes
Ling, Yong,Lu, Lingyi,Qiu, Xiaodong,Wang, Haoran,Zhang, Yanan,Zhou, Li
, p. 37083 - 37088 (2021/12/07)
A new one pot protocol has been developed for the reductive silylation of alkenyl methyl ethers using Et3Si-BPin and HSiEt3 with nickel(ii) catalyst. Styrene type methyl ethers, multi-substituted vinyl methyl ethers, heterocycles and unconjugated vinyl ethers are all tolerated to form alkyl silanes. Mechanistic study reveals that it is a cascade of a C-O bond silylation and vinyl double bond hydrogenation process. Internal nucleophilic substitution or oxidative addition pathways were both acceptable for C-O bond cleavage. The acquired intermediate alkenyl silanes then proceeded through an unconventional reduction process thus providing alkyl silanes.
Copper-Photocatalyzed Hydrosilylation of Alkynes and Alkenes under Continuous Flow
Zhong, Mingbing,Pannecoucke, Xavier,Jubault, Philippe,Poisson, Thomas
supporting information, p. 11818 - 11822 (2021/07/10)
Herein, the photocatalytic hydrosilylation of alkynes and alkenes under continuous flow conditions is described. By using 0.2 mol % of the developed [Cu(dmp)(XantphosTEPD)]PF6 under blue LEDs irradiation, a large panel of alkenes and alkynes was hydrosilylated in good to excellent yields with a large functional group tolerance. The mechanism of the reaction was studied, and a plausible scenario was suggested.
