Application of bis(phosphinite) pincer nickel complexes to the catalytic hydrosilylation of aldehydes

Chang, Jiarui; Fang, Fei; Tu, Chenhao; Zhang, Jie; Ma, Nana; Chen, Xuenian

doi:10.1016/j.ica.2020.120088

Cited by 15 publications

(14 citation statements)

References 52 publications

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“…Gratifyingly, reduction of acetophenone was readily completed in 6 h at 70 °C using 5 mol% of catalyst (Table 3, entry 1). It must be mentioned that the same catalytic reaction using Guan's nickel catalyst required extended reaction times to obtain a conversion of 18 % (24 h at 70 °C) with 1 mol% catalyst loading [8c] . In our case, 92 % conversion was obtained after 13 h at 70 °C using 1 mol % catalyst loading.…”

Section: Resultsmentioning

confidence: 53%

Hydrosilylation of Carbonyl Compounds Catalyzed by a Nickel Complex Bearing a PBP Ligand

et al. 2021

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The efficient catalytic hydrosilylation of ketones and aldehydes has been investigated using a nickel pincer hydride complex supported by a diphosphino‐boryl ligand (PBP). It was found that the presence of the boryl group within the skeleton of the ligand has a beneficial effect on the catalytic activities observed for ketones compared to related pincer systems. The analysis of the reaction mechanism allows for the synthesis and characterization of a nickel alkoxide derivative by insertion of the carbonyl moiety into the Ni−H bond. Combined experimental and theoretical analysis (DFT) support a reaction mechanism that involves the initial formation of an alkoxide complex followed by reaction with the silane to release the corresponding silyl ether and regenerate the catalyst.

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Section: Resultsmentioning

confidence: 53%

Hydrosilylation of Carbonyl Compounds Catalyzed by a Nickel Complex Bearing a PBP Ligand

et al. 2021

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“…The mechanisms of transition metal complex catalyzed hydrosilylation have been widely investigated . For the hydrosilylation of aldehydes and ketones catalyzed by POCOP pincer platinum and nickel hydride complexes, the reactions proceed through CO bond insertion into the metal hydride bond to form alkoxide complexes that further react with silane to form the hydrosilylation products. , The corresponding thiolate complexes demonstrate higher catalytic activity than the hydride complexes against the hydrosilylation of CO and CN bonds; ,, the reactions also proceed through the above metal hydride insertion mechanism and the in situ generated thio species are supposed to be co-catalysts. The versatile ability of complex 1a to effectively catalyze the hydrosilylation of wide ranges of unsaturated carbon-heteroatom bonds implies that the reactions may follow a general mechanism.…”

Section: Resultsmentioning

confidence: 99%

PNCNP Pincer Platinum Chloride Complex as a Catalyst for the Hydrosilylation of Unsaturated Carbon-Heteroatom Bonds

et al. 2022

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A PNCNP pincer-ligated platinum(II) chloride complex [2,6-( t Bu 2 PNH) 2 C 6 H 3 ]PtCl (1a) was synthesized and fully characterized. Complex 1a was applied to the catalytic hydrosilylation of unsaturated carbon-heteroatom bonds. For comparison, the corresponding hydride complex [2,6-( t Bu 2 PNH) 2 C 6 H 3 ]PtH (1b) and the related POCOP pincer chloride complex [2,6-( t Bu 2 PO) 2 C 6 H 3 ]PtCl (1c) were also used to catalyze the reactions. It was found that 1a is a good catalyst for the hydrosilylation of both C�O and C�N bonds. Wide ranges of aldimines, ketimines, aldehydes, and ketones were hydrosilylated, and the expected amine or alcohol products were obtained in good to excellent yields. The reactions also feature good functional group compatibility. Complex 1a represents the most effective transition metal catalyst for the hydrosilylation of the C�N bond and is among the best transition metal catalysts for the hydrosilylation of the C�O bond. The reactions are likely catalyzed by a cationic platinum(II) species generated from complex 1a during the reactions.

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“…For many years, we have been working in the area of the structure, reactivity and catalytic applications of group 10 metal complexes supported by different types of pincer ligands. During our investigation, we noticed that many hydroboration and hydrosilylation of aldehydes, ketones and imines catalyzed by pincer ligated group 10 metal hydride complexes [33,34,40,44,54] can also be catalyzed by the corresponding thiolate complexes [48,49,54–57] . Most importantly, the thiolate complexes usually exhibit higher catalytic activity than the hydride complexes.…”

Section: Introductionmentioning

confidence: 87%

“…Bisphosphinite‐based POCOP pincer nickel and platinum hydride complexes [40,44] and the corresponding thiolate complexes [55,57] are all active in catalyzing the hydrosilylation of aldehydes. Diphosphino‐boryl‐based PBP pincer platinum hydride and the corresponding thiolate complexes are also active in catalyzing this type of reaction [55] .…”

Section: The Catalytic Activities Of the Thiolate And The Hydride Com...mentioning

confidence: 99%

“…Ketones are usually more difficult to be hydrosilylated than aldehydes because the carbon center in a ketone molecule is sterically hindered compared to that in an aldehyde molecule. The above mentioned POCOP pincer nickel thiolate and hydride complexes, which are good catalysts for the hydrosilylation of aldehydes, were found to be inactive or far less active in catalyzing the hydrosilylation of ketones [40,57] . Nevertheless, the related third row platinum hydride and thiolate complexes are good catalysts in catalyzing the above reaction [44,55] .…”

Section: The Catalytic Activities Of the Thiolate And The Hydride Com...mentioning

confidence: 99%

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Notable Catalytic Activity of Transition Metal Thiolate Complexes against Hydrosilylation and Hydroboration of Carbon‐Heteroatom Bonds

Fang

Zhang

2023

Chemistry An Asian Journal

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Chemists tend to use transition metal hydride complexes rather than thiolate complexes to catalyse chemical transformations because the hydride complexes possess diverse catalytic reactivity, although most of them are air/ moisture-sensitive and difficult to prepare. By comparing the catalytic performances of pincer ligated group 10 metal thiolate and hydride complexes in catalysing the hydroboration and hydrosilylation of C=O and C=N bonds, we demonstrate in this review that transition metal thiolate complexes are much better catalysts than the corresponding hydride complexes in catalysing this type of reactions. Many hydroboration and hydrosilylation reactions catalysed by pincer ligated group 10 metal hydride complexes can also be catalysed by the corresponding thiolate complexes and the thiolate systems are far more active. Therefore, the applications of transition metal thiolate complexes in the catalytic hydroboration and hydrosilylation of unsaturated carbonheteroatom bonds deserve special attention in future work.

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Application of bis(phosphinite) pincer nickel complexes to the catalytic hydrosilylation of aldehydes

Cited by 15 publications

References 52 publications

Hydrosilylation of Carbonyl Compounds Catalyzed by a Nickel Complex Bearing a PBP Ligand

Hydrosilylation of Carbonyl Compounds Catalyzed by a Nickel Complex Bearing a PBP Ligand

PNCNP Pincer Platinum Chloride Complex as a Catalyst for the Hydrosilylation of Unsaturated Carbon-Heteroatom Bonds

Notable Catalytic Activity of Transition Metal Thiolate Complexes against Hydrosilylation and Hydroboration of Carbon‐Heteroatom Bonds

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