Dehydrogenative silylation of alcohols catalysed by half-sandwich iron N-heterocyclic carbene complexes

Cardoso, João M. P.; Lopes, Rita; Royo, Beatriz

doi:10.1016/j.jorganchem.2014.06.005

Cited by 43 publications

(18 citation statements)

References 50 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In the 31 P NMR spectra of these three comScheme 2. Synthesis of hydridoiron complexes 6-8 through selective C-H bond activation.…”

Section: Selective Activation Of C-h Bondsmentioning

confidence: 99%

“…This indicates that the ratio of imine ligand to PMe 3 is 1:1 in 14. In the 31 P NMR spectrum of 14, there is only one signal at δ = 10.3 ppm. Therefore, it can concluded that 14 has an octahedral coordination geometry around the iron atom with two phosphorus atoms at the axial positions and two imine ligands in the equatorial plane.…”

Section: Selective C-f Bond Activationmentioning

confidence: 99%

“…According to previous reports, iron complexes play significant roles in the hydrosilylation reactions of aldehydes, ketones, [21] alkenes, [22] alkynes, [23] amides, [24] esters, [25] and even CO 2 . [26] In addition, hydrogenation reactions of carbonyl compounds with H 2 as the hydrogenation source, [27] hydroboration reactions, [28] transfer hydrogenation reactions, [29] reductive amination reactions [30] and dehydrogenative silylation reactions of alcohols [31] can also be catalyzed by iron complexes. Among them, iron hydrides have been intensively studied in recent years owing to their catalytic activity in the hydrosilylation reactions of aldehydes and ketones.…”

Section: The Reduction Reactions Of Aldehydes and Ketones Catalyzed Bmentioning

confidence: 99%

See 2 more Smart Citations

Synthesis of Iron Hydrides by Selective C–F/C–H Bond Activation in Fluoroarylimines and Their Applications in Catalytic Reduction Reactions

Wang

Sun

2015

Eur J Inorg Chem

View full text Add to dashboard Cite

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.

show abstract

“…In the 31 P NMR spectra of these three comScheme 2. Synthesis of hydridoiron complexes 6-8 through selective C-H bond activation.…”

Section: Selective Activation Of C-h Bondsmentioning

confidence: 99%

Section: Selective C-f Bond Activationmentioning

confidence: 99%

Section: The Reduction Reactions Of Aldehydes and Ketones Catalyzed Bmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis of Iron Hydrides by Selective C–F/C–H Bond Activation in Fluoroarylimines and Their Applications in Catalytic Reduction Reactions

Wang

Sun

2015

Eur J Inorg Chem

View full text Add to dashboard Cite

show abstract

“…Over the years, direct dehydrogenative coupling of alcohols with hydrosilanes emerged as a green, halogen-free alternative to the former approach. At the moment, it can be catalyzed by a wide range of compounds including both transition metal complexes [15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] and simple inorganics and organocatalysts [31][32][33][34][35]. As the only byproduct of these reaction is molecular hydrogen, they are also considered chemical storage of this element [36], whose capacity greatly varies with the silane being used and can be as high as over 4 wt % [16].…”

Section: Introductionmentioning

confidence: 99%

Direct Dehydrogenative Coupling of Alcohols with Hydrosilanes Promoted by Sodium tri(sec-butyl)borohydride

et al. 2018

View full text Add to dashboard Cite

Alkoxysilanes find application in many areas of chemistry ranging from research-scale organic synthesis to multi-ton production of materials. Classically, they are obtained in stoichiometric reaction of alcoholysis of chlorosilanes, however, recent years brought development in the field of direct dehydrogenative coupling of hydrosilanes with alcohols, which is a more atom-economic and benign alternative to the former process. In this paper, we report the use of sodium tri(sec-butyl)borohydride as a convenient promoter of this reaction. Exemplary syntheses carried out under mild conditions and without additional solvents, followed by very easy work-up procedure, show excellent potential for application of so devised catalytic system.

show abstract

“…Mechanistic studies suggest the formation of hydrogen bonds between the NHC and the alcohol (Scheme ). Moreover, three independent groups show that iron, iridium, and nickel NHC complexes can also catalyze Si−O coupling.…”

Section: Silicon–oxygen Bond Formationmentioning

confidence: 99%

Catalytic Formation of Silicon–Heteroatom (N, P, O, S) Bonds

Kuciński

Hreczycho

2017

ChemCatChem

View full text Add to dashboard Cite

Silicon and its compounds with other heteroatoms have received considerable attention, particularly because of their applicative ability. Silicon forms a large number of compounds with other p‐block elements (e.g., C, N, S, O, F, Cl, and others). All of them affect practical chemistry to some extent and are characterized by unique properties. This article highlights recent developments and covers the literature from the last 10 years. It is mainly focused on catalytic methods for silicon–nitrogen, silicon–phosphorus, silicon–oxygen, and silicon–sulfur bond formation. The scope and applications of these practical compounds will also be discussed.

show abstract

Dehydrogenative silylation of alcohols catalysed by half-sandwich iron N-heterocyclic carbene complexes

Cited by 43 publications

References 50 publications

Synthesis of Iron Hydrides by Selective C–F/C–H Bond Activation in Fluoroarylimines and Their Applications in Catalytic Reduction Reactions

Synthesis of Iron Hydrides by Selective C–F/C–H Bond Activation in Fluoroarylimines and Their Applications in Catalytic Reduction Reactions

Direct Dehydrogenative Coupling of Alcohols with Hydrosilanes Promoted by Sodium tri(sec-butyl)borohydride

Catalytic Formation of Silicon–Heteroatom (N, P, O, S) Bonds

Contact Info

Product

Resources

About