122205-40-7

Upstream product

• 998-30-1 Triethoxysilane 
• 123-11-5 4-methoxy-benzaldehyde 
• 100-52-7 benzaldehyde 

Downstream Products

• 105-13-5 4-Methoxybenzyl alcohol 

Relevant academic research and scientific papers

Synthesis, characterization and reactivity of iron- and cobalt-pincer complexes

The tBuPONOP (2,6-bis(di-tert-butyl-phosphinito)pyridine) complexes of iron and cobalt, (tBuPONOP)FeCl2 (1) and (tBuPONOP)CoCl2 (2)) have been prepared. Both complexes are paramagnetic and the solid-state structures of 1 and 2 were determined by single crystal X-ray diffraction studies. Analogous Fe and Co complexes of the tBuPNP (2,6-bis(di-tert-butyl-phosphinomethyl)pyridine) ligand (3 and 4, respectively) were prepared to allow comparison between the closely related pincer ligands in the hydrosilylation of carbonyl moieties. All four complexes were found to be catalytically active when treated with NaBEt3H, which was assumed to generate a metal-hydride species in-situ.

Synthesis and catalytic activity of N-heterocyclic silylene (NHSi) iron (II) hydride for hydrosilylation of aldehydes and ketones

A novel silylene supported iron hydride [Si, C]FeH (PMe3)3 (1) was synthesized by C (sp3)-H bond activation with zero-valent iron complex Fe (PMe3)4. Complex 1 was fully characterized by spectroscopic methods and single crystal X-ray diffraction analysis. To the best of our knowledge, 1 is the first example of silylene-based hydrido chelate iron complex produced through activation of the C (sp3)?H bond. It was found that complex 1 exhibited excellent catalytic activity for hydrosilylation of aldehydes and ketones. The catalytic system showed good tolerance and catalytic activity for the substrates with different functional groups on the benzene ring. It is worth mentioning that, the experimental results showed that both ketones and aldehydes could be reduced in good to excellent yields under the same catalytic conditions. Based on the experiments and literature reports, a possible catalytic mechanism was proposed.

New Zinc Catalyst for Hydrosilylation of Carbonyl Compounds

A new zinc complex was synthesized and applied in the catalytic hydrosilylation of carbonyl compounds. Optimization of the reaction conditions showed that the presence a substoichiometric amount of methanol accelerates the process significantly. The reaction can proceed at very low catalyst load (down to 0.1 molpercent) under mild reaction conditions. The reaction tolerates the presence of C=C bonds, and thus can be useful for the synthesis of allylic alcohols from α,β-unsaturated aldehydes and ketones.

Synthesis of silyl iron hydride: Via Si-H activation and its dual catalytic application in the hydrosilylation of carbonyl compounds and dehydration of benzamides

The hydrido silyl iron complex (o-Ph2PC6H4SiMe2)Fe(PMe3)3H (2) was obtained via the activation of the Si-H bond of the bidentate silyl ligand o-Ph2P(C6H4)SiMe2H (1) by Fe(PMe3)4. 2 showed good to excellent catalytic activity in both the reduction of aldehydes/ketones and the dehydration of benzamide. In addition, with complex 2 as a catalyst, α,β-unsaturated carbonyls could be selectively reduced to the corresponding α,β-unsaturated alcohols. The mechanisms of the formation of 2 and the catalytic dehydration process are proposed and partly experimentally verified.

Syntheses of hydrido selenophenolato iron(II) complexes and their catalytic application in hydrosilylation of aldehydes and ketones

Three novel selenophenolato hydrido iron(II) complexes [cis-(H)(SeAr)Fe(PMe3)4] (4–6) (Ar=C6H5 (4), p-MeOC6H4 (5) and o-MeC6H4 (6)) were prepared through the reaction of Fe(PMe3)4 with selenophenols ArSeH (1–3) via Se–H activation. The iron hydrido complexes 4, 5 and 6 could catalyze the hydrosilylation of aldehydes and ketones. Among them complex 5 is the best catalyst for this process. Furthermore, α,β-unsaturated alcohols could be obtained from the selective reduction reactions of the corresponding α,β-unsaturated carbonyls catalyzed by hydrido iron(II) complex 5. This catalytic system has good tolerance for some common groups but it is easy to reduce the nitro group to an amino group. The experiments indicate that the chemoselectivity for this catalytic system is –CHO>–NO2>–C([dbnd]O)CH3. The crystal structure of 6 was determined by X-ray diffraction.

Synthesis and catalytic application of [PPP]-pincer iron, nickel and cobalt complexes for the hydrosilylation of aldehydes and ketones

A new synthetic strategy for the novel diphosphine-phosphine oxide ligand (1) (Ph2P-(C6H4))2P(O)H was designed. A series of [PPP]-pincer Fe, Ni, and Co complexes were prepared. All of them were formed by chelate-assisted P-H activation. Two metal hydrides [(Ph2P-(C6H4))2P(O)]Fe(H)(PMe3)2 (2) and [(Ph2P-(C6H4))2P(O)]Ni(H)(PMe3) (3) were obtained at room temperature. The combination of ligand 1 with Co(PMe3)4Me or Co(PMe3)4 afforded the same Co(i) complex [(Ph2P-(C6H4))2P(O)]Co(PMe3)2 (4) via P-H bond activation. The catalytic performance of the Fe, Ni, and Co complexes for the hydrosilylation of aldehydes and ketones was explored. At a catalyst loading of 2 mol%, complex 2 displayed the best catalytic activity for the hydrosilylation by using (EtO)3SiH as the hydrogen source under mild conditions. Complexes 2, 3, and 4 were characterized by spectroscopic methods and X-ray diffraction analysis.

Preparation of hydrido [CNC]-pincer cobalt complexes via selective C-H/C-F bond activation and their catalytic performances

Polyfluorinated aryl imines 2,4,5-R1,R2,R3-C6H2-HC═N-1-C10H7 (R1 = F, R2 = F, R3 = H (1); R1 = F, R2 = H, R3 = F (2) and R1 = F, R2 = F, R3 = F (3)) and F5C6-HC═N-1-C10H7 (7) reacted with CoMe(PMe3)4 to give rise to hydrido [CNC]-pincer cobalt(iii) complexes (2,4,5-R1,R2,R3-C6H-HC═N-1-C10H6)Co(H)(PMe3)2 (R1 = F, R2 = F, R3 = H (4); R1 = F, R2 = H, R3 = F (5); R1 = F, R2 = F, R3 = F (6)) and (F4C6-HC═N-1-C10H6)Co(H)(PMe3)2 (8) via selective C-F/C-H bond activation. Penta-coordinate dicarbonyl cobalt(i) complexes (2,4,5-R1,R2,R3-C6H-HC═N-1-C10H7)Co(CO)2(PMe3) (R1 = F, R2 = H, R3 = F (9); R1 = F, R2 = F, R3 = F (10)) were obtained from reactions of hexa-coordinate cobalt(iii) complexes 5 and 6 with carbon monoxide through reductive elimination. Cobalt(iii) halides (2,4,5-R1,R2,R3-C6H-HC═N-1-C10H6)Co(i)(PMe3)2 (R1 = F, R2 = F, R3 = H (11); R1 = F, R2 = H, R3 = F (12); R1 = F, R2 = F, R3 = F (13)) and (2,4,5-R1,R2,R3-C6H-HC═N-1-C10H6)Co(Br)(PMe3)2 (R1 = F, R2 = F, R3 = H (14); R1 = F, R2 = H, R3 = F (15); R1 = F, R2 = F, R3 = F (16)) were prepared by the interaction between hydrido cobalt(iii) complexes 4-6 and MeI or EtBr. The molecular configurations of complexes 4, 8, and 11 were determined by single crystal X-ray diffraction. We then confirmed that the four hydrido cobalt(iii) complexes 4-6 and 8 could be used as catalysts for reduction of aldehydes and ketones. Complex 8 is the best catalyst among the four complexes and can selectively catalyze the carbonyl groups of α,β-unsaturated aldehydes and ketones.

Synthesis of [POCOP]-pincer iron and cobalt complexes via Csp3-H activation and catalytic application of iron hydride in hydrosilylation reactions

Csp3-H bond activation in diphosphinito pincer ligand (Ph2PO(o-C6H2-(4,6-tBu2)))2CH2 (1) (POCH2OP) was achieved by Fe(PMe3)4 and CoMe(PMe3)4 to afford complexes (POCHOP)Fe(H) (PMe3)2 (2) and (POCHOP)Co(PMe3)2 (4) under mild conditions. Hydrido iron complex 2 reacted with iodomethane via the elimination of methane to deliver complex (POCHOP)FeI(PMe3) (3). The ligand replacement in Ni(PMe3)4 by 1 gave rise to nickel(0) complex (POCH2OP)Ni(PMe3)2 (5) without Csp3-H bond activation of the pincer ligand (1). It was confirmed that the hydrosilylation of aldehydes and ketones could be effectively catalyzed by hydrido iron complex 2. Complexes 2-5 were characterized by spectroscopic methods and X-ray single crystal diffraction analysis. This journal is

Synthesis of iron hydrides by selective C-F/C-H bond activation in fluoroarylimines and their applications in catalytic reduction reactions

The reactions of Fe(PMe3)4 with different 2,6-diflurophenylarylimines 1-5 were explored. Fluoroarylimines 1-3, the aryl rings of which are substituted with electron-withdrawing groups, reacted with Fe(PMe3)4 to afford the C-H activation products 6-8. However, if the aryl rings of the fluoroarylimines were substituted with electron-donating groups, the iron hydrides 9 and 10 were obtained from the reactions of the fluoroarylimines with Fe(PMe3)4 through C-F bond activation. In a further study, silanes, especially triethoxysilane, were found to benefit the reactions and improve the yields of the hydridoiron complexes. The three-component reaction of Fe(PMe3)4, a fluoroarylimine, and a silane could also be utilized in reactions involving 2,6-(CH3)2C6H3-C(=NH)-2,6-F2C6H3 (13) and 2,6-F2C6H3-C(=NH)-C6F5 (16) to synthesize iron hydrides (15 and 18). The hydridoiron complexes could be utilized as efficient catalysts in the hydrosilylation of aldehydes and ketones. Furthermore, cinnamaldehydes were selectively reduced to the corresponding cinnamyl alcohols in high yields. The mechanism of the catalytic reduction reaction was studied extensively through operando IR spectroscopy.

A cationic zinc hydride cluster stabilized by an N-heterocyclic carbene: Synthesis, reactivity, and hydrosilylation catalysis

The trinuclear cationic zinc hydride cluster [(IMes)3Zn3H4 (THF)](BPh4)2 (1) was obtained either by protonation of the neutral zinc dihydride [(IMes)ZnH2]2 with a Bronsted acid o