136795-58-9

Upstream product

• 111-66-0 oct-1-ene 
• 775-12-2 diphenylsilane 
• 13389-42-9 trans-2-Octene 
• 14919-01-8 (E)-3-octene 
• 694-53-1 phenylsilane 
• 111-67-1 2-octene 

Relevant academic research and scientific papers

Metal-free photocatalytic hydrosilylation of olefins in the presence of photoinitiators

A convenient metal-free photocatalytic hydrosilylation of a variety of linear and cyclic alkenes has been investigated. It was found that the free radical type photoinitiator Irgacure 2959 had a better effect on the hydrosilylation reaction; using 3 mol%

Phosphine-iminopyridines as platforms for catalytic hydrofunctionalization of alkenes

A series of phosphine-diimine ligands were synthesized by the condensation of 2-(diphenylphosphino)aniline (PNH2) with a variety of formyl and ketopyridines. Condensation of PNH2 with acetyl- and benzoylpyridine yielded the Ph2P(C6H4)N=C(R)(C5H4N), respectively abbreviated PNMepy and PNPhpy. With ferrous halides, PNPhpy gave the complexes FeX2(PNPhpy) (X = Cl, Br). Condensation of pyridine carboxaldehyde and its 6-methyl derivatives with PNH2 was achieved using a ferrous template, affording low-spin complexes [Fe(PNHpyR)2]2+ (R = H, Me). Dicarbonyls Fe(PNRpy)(CO)2 were produced by treating PNMepy with Fe(benzylideneacetone)(CO)3 and reduction of FeX2(PNPhpy) with NaBEt3H under a CO atmosphere. Cyclic voltammetric studies show that the [FeL3(CO)2]0/- and [FeL3(CO)2]+/0 couples are similar for a range of tridentate ligands, but the PNPhpy system uniquely sustains two one-electron reductions. Treatment of Fe(PNPhpy)X2 with NaBEt3H gave active catalysts for the hydroboration of 1-octene with pinacolborane. Similarly, these catalysts proved active for the addition of diphenylsilane, but not HSiMe(OSiMe3)2, to 1-octene and vinylsilanes. Evidence is presented that catalysis occurs via iron hydride complexes of intact PNPhpy.

Hydrosilylation of Ketones Catalyzed by Iron Iminobipyridine Complexes and Accelerated by Lewis Bases

Fe-iminobipyridine complexes ((RBPIAr,R′)FeBr2, RBPIAr,R′=iminobipyridine derivatives) were found to exhibit good catalytic activity for hydrosilylation of ketones. The highest TOF (turnover frequency

Chemoselective Hydrosilylation of Olefin/Ketone Catalyzed by Iminobipyridine Fe and Co complexes

The chemoselective hydrosilylation of olefins and ketones catalyzed by Fe and Co complexes bearing an iminobipyridine derivative ligand was investigated. The reaction of a 1 : 1 mixture of styrene and acetophenone over the Fe catalyst achieved selective h

The Effect of Substituents on the Formation of Silyl [PSiP] Pincer Cobalt(I) Complexes and Catalytic Application in Both Nitrogen Silylation and Alkene Hydrosilylation

Four different [PSiP]-pincer ligands L1-L4 ((2-Ph2PC6H4)2SiHR (R = H (L1) and Ph (L2)) and (2-iPr2PC6H4)2SiHR′ (R′ = Ph (L3) and H (L4)) were used to investigate the effect of substituents at P and/or Si atom of the [PSiP] pincer ligands on the formation of silyl cobalt(I) complexes by the reactions with CoMe(PMe3)4 via Si-H cleavage. Two penta-coordinated silyl cobalt(I) complexes, (2-Ph2PC6H4)2HSiCo(PMe3)2 (1) and (2-Ph2PC6H4)2PhSiCo(PMe3)2 (2), were obtained from the reactions of L1 and L2 with CoMe(PMe3)4, respectively. Under similar reaction conditions, a tetra-coordinated cobalt(I) complex (2-iPr2PC6H4)2PhSiCo(PMe3) (3) was isolated from the interaction of L3 with CoMe(PMe3)4. It was found that, only in the case of ligand L4, silyl dinitrogen cobalt(I) complex 4, [(2-iPr2PC6H4)2HSiCo(N2)(PMe3)], was formed. Our results indicate that the increasing of electron cloud density at the Co center is beneficial for the formation of a dinitrogen cobalt complex because the large electron density at Co center leads to the enhancement of the ?-backbonding from cobalt to the coordinated N2. It was found that silyl dinitrogen cobalt(I) complex 4 is an effective catalyst for catalytic transformation of dinitrogen into silylamine. Among these four silyl cobalt(I) complexes, complex 1 is the best catalyst for hydrosilylation of alkenes with excellent regioselectivity. For aromatic alkenes, catalyst 1 provided Markovnikov products, while for aliphatic alkenes, anti-Markovnikov products could be obtained. Both catalytic reaction mechanisms were proposed and discussed. The molecular structures of complexes 1-4 were confirmed by single-crystal X-ray diffraction.

Cobalt bis(2-ethylhexanoate) and terpyridine derivatives as catalysts for the hydrosilylation of olefins

A simple method for the hydrosilylation of olefins by using air-stable cobalt catalysts is developed. The catalyst system is composed of simple, cheap, and readily available cobalt(II) salts and well-defined terpyridine derivatives as cocatalysts or ligands, and the hydrosilylation processes can be processed smoothly under mild conditions without either Grignard reagents or NaHBEt3 as activator.

Catalytic hydrosilylation of olefins and ketones by base metal complexes bearing a 2,2′:6′,2″-terpyridine ancillary ligand

The activities of [M(tpy)Br2] (M = Mn, Co, Ni, or Cu) for the hydrosilylation of olefins and ketones were investigated in the presence of NaBHEt3 as an activator. [Co(tpy)Br2] and [Ni(tpy)Br2] showed catalytic a

A Bottleable Imidazole-Based Radical as a Single Electron Transfer Reagent

Reduction of 1,3-bis(2,6-diisopropylphenyl)-2,4-diphenyl-1H-imidazol-3-ium chloride (1) resulted in the formation of the first structurally characterized imidazole-based radical 2. 2 was established as a single electron transfer reagent by treating it with an acceptor molecule tetracyanoethylene. Moreover, radical 2 was utilized as an organic electron donor in a number of organic transformations such as in activation of an aryl-halide bond, alkene hydrosilylation, and in catalytic reduction of CO2 to methoxyborane, all under ambient temperature and pressure.

Selectivity Reverse of Hydrosilylation of Aryl Alkenes Realized by Pyridine N-Oxide with [PSiP] Pincer Cobalt(III) Hydride as Catalyst

Six silyl cobalt(III) hydrides 1-6 with [PSiP] pincer ligands having different substituents at the P and Si atoms ([(2-Ph2PC6H4)2MeSiCo(H)(Cl)(PMe3)] (1), [(2-Ph2PC6H4)2HSiCo(H)(Cl)(PMe3)] (2), [(2-Ph2PC6H4)2PhSiCo(H)(Cl)(PMe3)] (3), [(2-iPr2PC6H4)2HSiCo(H)(Cl)(PMe3)] (4), [(2-iPr2PC6H4)2MeSiCo(H)(Cl)(PMe3)] (5), and [(2-iPr2PC6H4)2PhSiCo(H)(Cl)(PMe3)] (6)) were synthesized through the reactions of the ligands (L1-L6) with CoCl(PMe3)3 via Si-H bond cleavage. Compounds 1-6 have catalytic activity for alkene hydrosilylation, and among them, complex 3 is the best catalyst with excellent anti-Markovnikov regioselectivity. A silyl dihydrido cobalt(III) complex 7 from the reaction of 3 with Ph2SiH2 was isolated, and its catalytic activity is equivalent to that of complex 3. Complex 7 and its derivatives 10-12 could also be obtained through the reactions of complexes 3, 1, 4, and 5 with NaBHEt3. The molecular structure of 7 was indirectly verified by the structures of 10-12. To our delight, the addition of pyridine N-oxide reversed the selectivity of the reaction, from anti-Markovnikov to Markovnikov addition. At the same time, the reaction temperature was reduced from 70 to 30 °C on the premise of high yield and excellent selectivity. However, this catalytic system is only applicable to aromatic alkenes. On the basis of the experimental information, two reaction mechanisms are proposed. The molecular structures of cobalt(III) complexes 3-6 and 10-12 were determined by single crystal X-ray diffraction analysis.

-Chelate Cobalt(III) Hydride Catalyzed Hydrosilylation of Alkenes

Bidentate ligand 2-diphenylphosphinobenzaldehyde or 2-diisopropylphosphinobenzaldehyde reacted with CoCl(PMe3)3 to give [P,C]-chelate cobalt(III) hydrides [mer-(Me3P)3Co(H)(Cl)(o-Ph2P-C6H4-C═O)] (1) or [mer-(Me3P)3Co(H)(Cl)(o-iPr2P-C6H4-C═O)] (2), respectively. Complex 2 was new and characterized by spectroscopic methods and single-crystal X-ray diffraction analysis. It was found that both complex 1 and 2 are active catalysts for hydrosilylation of alkenes. Although the catalytic activity of 1 is slightly higher, catalyst 1 and 2 have the same selectivity. The selectivity for aromatic alkenes is mainly of the Markovnikov type, while the selectivity for aliphatic alkenes is almost 100% anti-Markovnikov type. In the study of the reaction mechanism, a silyl cobalt dihydride [(Ph2ClSi)Co(H)2(PMe3)3] was isolated from the stoichiometric reaction of hydride 1 with Ph2SiH2. The catalytic mechanism for alkene hydrosilylation with [HCo(PMe3)3] as a real catalyst is proposed and discussed with the experimental results.