122205-35-0

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• 998-30-1 Triethoxysilane 
• 459-57-4 4-fluorobenzaldehyde 

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• 459-56-3 4-fluorobenzylic alcohol 

Relevant academic research and scientific papers

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 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.

Cobalt POCOP Pincer Complexes via Ligand C-H Bond Activation with Co2(CO)8: Catalytic Activity for Hydrosilylation of Aldehydes in an Open vs a Closed System

A series of cobalt POCOP pincer complexes with the formulas {2,6-(iPr2PO)2-4-R′-C6H2}Co(CO)2 (R′ = H (1a), NMe2 (1b), OMe (1c), CO2Me (1d)), {2,6-(Ph2PO)2C6H3}Co(CO)2 (1e), and {2,6-(tBu2PO)2C6H3}Co(CO) (2f) have been synthesized through C-H bond activation of the corresponding pincer ligands with Co2(CO)8. These complexes have been demonstrated to catalyze the hydrosilylation of PhCHO with (EtO)3SiH, which exhibits an induction period and the decreasing reactivity order 1b > 1c > 1a > 1d > 1e. The catalytic protocol can be applied to various aldehydes with turnover numbers of up to 300. The CO ligands in the dicarbonyl complexes have been shown to exchange with 13CO at room temperature and partially dissociate from cobalt at high temperatures. Substitution of CO by tert-butyl isocyanide has been accomplished with 1a at 50-80 °C, resulting in the formation of {2,6-(iPr2PO)2C6H3}Co(CNtBu)(CO) (3a) and {2,6-(iPr2PO)2C6H3}Co(CNtBu)2 (4a). The catalytic reactions are more efficient when they are carried out in an open system or if the catalysts are preactivated by the aldehydes. The structures of 1a-e, 3a, and 4a have been studied by X-ray crystallography.

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 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

Synthesis and catalytic application in hydrosilylation of the complex mer-hydrido(2-mercaptobenzoyl)tris(trimethylphosphine)cobalt(III)

The sulfur-coordinated acyl(hydrido)cobalt(III) complex 1 was synthesized by reaction of thiosalicylaldehyde with CoMe(PMe3)4. The crystal structure of 1 was determined by X-ray diffraction. Complex 1 is an excellent catalyst for the hydrosilylation of aldehydes and ketones under mild conditions. This might be the first example of hydrosilylation of aldehydes and ketones catalyzed by (hydrido)cobalt complexes.

Iron hydride complexes bearing phosphinite-based pincer ligands: Synthesis, reactivity, and catalytic application in hydrosilylation reactions

Treatment of resorcinol-derived bis(phosphinite) ligands 1,3-(R 2PO)2C6H4 (R = iPr and Ph) with Fe(PMe3)4 furnishes iron POCOP-pincer hydride complexes [2,6-(R2PO)2C6H3]Fe(H) (PMe3)2 (R = iPr, 1a; R = Ph, 1b) with two PMe3cis to each other. The isopropyl complex 1a undergoes ligand substitution upon mixing with CO to give [2,6-(iPr 2PO)2C6H3]Fe(H)(PMe 3)(CO). The kinetic product (2a) of this process contains a CO ligand trans to the hydride, whereas the thermodynamic product (2a′) has a CO ligand cis to the hydride. The displacement of PMe3 in 2a by CO takes place at an elevated temperature, resulting in the formation of [2,6-( iPr2PO)2C6H3]Fe(H)(CO) 2 (3a). These new iron POCOP-pincer hydride complexes catalyze the hydrosilylation of aldehydes and ketones with different functional groups, and 1a is the most efficient catalyst for this process. Isotopic labeling experiments rule out the hydride ligand being directly involved in the reduction. The hydrosilylation reactions are more likely to proceed via the activation of silanes or carbonyl substrates after ligand (PMe3, or CO in the case of 3a) dissociation from the iron center.