Cyclopentadienyliron dicarbonyl dimer: A simple tool for the hydrosilylation of aldehydes and ketones under air

Jung, Thais Cordeiro; Argouarch, Gilles; Weghe, Pierre van de

doi:10.1016/j.catcom.2016.01.033

Cited by 15 publications

(1 citation statement)

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“…In 2016, Jung et al reported the successful application of the readily available iron complex [CpFe(CO) 2 ] 2 as a catalyst for the hydrosilylation of aldehydes and ketones. 68 Optimized conditions required a 5 mol % loading of the iron precursor, in the presence of 2 equiv of (EtO) 2 MeSiH, at 100 °C during 24 h. Remarkably, the reaction worked well under air and no solvent was needed either. Under these conditions, both aldehydes and ketones (most of them aromatic) afforded excellent or quantitative conversions.…”

Section: Iron-based Catalystsmentioning

confidence: 99%

Iron-Catalyzed Homogeneous Hydrosilylation of Ketones and Aldehydes: Advances and Mechanistic Perspective

2019

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This review is focused on iron-based homogeneous catalytic systems described so far for the reduction of carbonyl compounds (ketones and aldehydes) into alcohols via hydrosilylation. It begins explaining the basic concepts of the hydrosilylation reaction, addressing its main advantages and procedural differences with other common reduction methods, and highlighting its interest in organic chemistry. Then, the advances in the development of iron-based catalysts, as a more sustainable alternative to the traditional noble-metal catalysts, that have taken place to date are reviewed in depth. The revision of the different type of catalysts is followed by a profound discussion of the mechanistic proposals found in the literature for this type of catalysts. KEYWORDS. hydrosilylation, reduction of carbonyls, homogeneous catalysis, iron, carbonyl compounds, mechanistic studies catalysts react, thus allowing the development of better catalytic systems via improving the designs 750 of both ligands and complexes. 751 752 AUTHOR INFORMATION 753

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Section: Iron-based Catalystsmentioning

confidence: 99%

Iron-Catalyzed Homogeneous Hydrosilylation of Ketones and Aldehydes: Advances and Mechanistic Perspective

2019

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Hydrosilylation of Aldehydes and Ketones Catalysed by Bis(phosphinite) Pincer Platinum Hydride Complexes

et al. 2020

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Bis(phosphinite) pincer platinum hydride complexes, [2,6‐(R2PO)2C6H3]PtH (R=tBu, iPr), were synthesized, characterized and applied to the hydrosilylation of aldehydes and ketones. NMR study and single crystal X‐ray diffraction analysis indicated that the hydrides in these two platinum complexes are comparatively less hydridic: down‐field 1H NMR resonances (0.71 and 0.98 ppm) and weak Pt−H interactions were observed. Both the platinum complexes were found to be good catalysts for the hydrosilylation of aldehydes and ketones with phenylsilane. The corresponding alcohols were isolated in good to excellent yields following basic hydrolysis of the resultant hydrosilylation products and turnover frequencies (TOFs) up to 3200 h−1 were achieved at 60 °C in toluene, which are much higher than those of the hydrosilylation catalysed by the corresponding nickel pincer hydride complexes. A possible mechanism for the present hydrosilylation process was discussed.magnified image

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Regioselective Nucleophilic Additions to Diiron Carbonyl Complexes Containing a Bridging Aminocarbyne Ligand: A Synthetic, Crystallographic and DFT Study

et al. 2017

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Diiron μ-aminocarbyne compounds, 1a-e, are prepared in two steps from Fe 2 Cp 2 (CO) 4 , negating the need for difficult purification procedures of intermediate species; they are efficiently isolated by alumina chromatography. Minor amounts of μ-aminocarbyne aryl isocyanide compounds, 2a-c, are obtained as side products. The structures of the cations in 1a,c,e are calculated using DFT; the carbyne carbon is generally predicted to be the thermodynamic site of hydride addition, in agreement with a previous experimental finding concerning 1a. Accordingly, the reaction of 1e with NaBH 4 affords a bridging aminocarbene complex, 4, in 85 % yield. Otherwise, the reaction of 1c with NaBH 4 yields the aminocarbyne-cyclopentadiene derivative 3 (70 %), presumably as a consequence of the [a] Scheme 1. Regioselective additions of nucleophiles to the diiron aminocarbyne complex 1a. Results and DiscussionThe commercial compound [Fe 2 Cp 2 (CO) 4 ] was reacted with the appropriate isocyanide, in a ca. 3:2 molar ratio, in acetonitrile solution. [16] The reactions with alkyl isocyanides were conducted under reflux conditions, whereas the reactions with aryl isocyanides proceeded at room temperature. The resulting mixtures were dried under vacuum and the residues were dissolved in dichloromethane and then treated with methyl triflate, thus affording the μ-aminocarbyne complexes 1a-e (Scheme 2). The difficult isolation of the monoisocyanide intermediates (see the Introduction) was unnecessary. The final products 1a-e were efficiently purified by alumina chromatography and were then isolated as microcrystalline, air-stable compounds in 65-92 % yields. The synthesis of 1c-e was accompanied by the side formation of minor products derived from di-isocyanide species, 2a-c. Compounds 2a-c were recovered by the chromatography in 3-12 % yields, although 2a was formerly reported as being Scheme 2. Synthesis of diiron μ-aminocarbyne complexes.Eur. J. Inorg. Chem. 2018, 960-971 www.eurjic.org

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Cyclopentadienyliron dicarbonyl dimer: A simple tool for the hydrosilylation of aldehydes and ketones under air

Abstract: International audienceThe readily available iron complex [CpFe(CO)2]2 (1) exhibits good catalytic activity in the hydrosilylation of aldehydes and ketones in the presence of diethoxymethylsilane. The procedure described is air-tolerant and applicable to a wide range of substrate

Cited by 15 publications

References 34 publications

Iron-Catalyzed Homogeneous Hydrosilylation of Ketones and Aldehydes: Advances and Mechanistic Perspective

Iron-Catalyzed Homogeneous Hydrosilylation of Ketones and Aldehydes: Advances and Mechanistic Perspective

Hydrosilylation of Aldehydes and Ketones Catalysed by Bis(phosphinite) Pincer Platinum Hydride Complexes

Regioselective Nucleophilic Additions to Diiron Carbonyl Complexes Containing a Bridging Aminocarbyne Ligand: A Synthetic, Crystallographic and DFT Study

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