102-24-9Relevant articles and documents
BH3 Activation by Phosphorus-Stabilized Geminal Dianions: Synthesis of Ambiphilic Organoborane, DFT Studies, and Catalytic CO2 Reduction into Methanol Derivatives
Lafage, Mathieu,Pujol, Anthony,Saffon-Merceron, Nathalie,Mézailles, Nicolas
, p. 3030 - 3035 (2016)
The reaction of the geminal dianion (SCS)2- 1 with 2 equiv of BH3·SMe2 leads to the isolation and full characterization of the new organoborane [(SCS)BH2][Li(THF)2] 2, in which the C=B bond possesses ambiphilic, multiple character. Treatment of 2 with another 1 equiv of BH3·SMe2 allows the isolation of the rare cyclic diborane species [(SCS)B2H5][Li(OEt2)] 4. The electronic structures of both compounds were investigated by means of DFT calculations. Compound 4 is an efficient catalyst for the reduction of CO2 to methanol derivatives by BH3·SMe2. A TON of ca. 2800 (TOF = 127 h-1) was achieved using 0.1 mol % of 4 in THF.
A highly active phosphine-borane organocatalyst for the reduction of CO2 to methanol using hydroboranes
Courtemanche, Marc-Andre,Legare, Marc-Andre,Maron, Laurent,Fontaine, Frederic-Georges
, p. 9326 - 9329 (2013)
In this work, we report that organocatalyst 1-Bcat-2-PPh2-C 6H4 ((1); cat = catechol) acts as an ambiphilic metal-free system for the reduction of carbon dioxide in presence of hydroboranes (HBR2 = HBcat (catecholborane), HBpin (pinacolborane), 9-BBN (9-borabicyclo[3.3.1]nonane), BH3·SMe2 and BH 3·THF) to generate CH3OBR2 or (CH 3OBO)3, products that can be readily hydrolyzed to methanol. The yields can be as high as 99% with exclusive formation of CH 3OBR2 or (CH3OBO)3 with TON (turnover numbers) and TOF (turnover frequencies) reaching >2950 and 853 h-1, respectively. Furthermore, the catalyst exhibits "living" behavior: once the first loading is consumed, it resumes its activity on adding another loading of reagents.
Organocatalysts with carbon-centered activity for CO2 reduction with boranes
Yang, Yanxin,Xu, Maotong,Song, Datong
, p. 11293 - 11296 (2015)
We report two organocatalysts for CO2 hydroboration to methylborylethers, which upon hydrolysis can produce methanol. These organocatalysts feature carbon-centered reversible CO2 binding, broad borane scopes, and high catalytic activities.
Reduction of CO2 to trimethoxyboroxine with BH3 in THF
Fujiwara, Koji,Yasuda, Shogo,Mizuta, Tsutomu
, p. 6692 - 6695 (2014)
Commercially available THF solutions of BH3·THF, which contain 0.5 mol % of NaBH4 as a stabilizing reagent for BH3·THF, react with 1 atm of CO2 at room temperature to form trimethoxyboroxine, (MeOBO)3, in 87% yield after 12 h. Since no reaction took place in the absence of NaBH4, NaBH4 was found to work as a promoter or catalyst for the reduction of CO2 with BH3 to the methoxy compound. A similar reaction using HCOONa in place of NaBH4 also gave (MeOBO)3 in comparable yield.
Transforming atmospheric CO2 into alternative fuels: A metal-free approach under ambient conditions
Chandra Sau, Samaresh,Bhattacharjee, Rameswar,Hota, Pradip Kumar,Vardhanapu, Pavan K.,Vijaykumar, Gonela,Govindarajan,Datta, Ayan,Mandal, Swadhin K.
, p. 1879 - 1884 (2019)
This work demonstrates the first-ever completely metal-free approach to the capture of CO2 from air followed by reduction to methoxyborane (which produces methanol on hydrolysis) or sodium formate (which produces formic acid on hydrolysis) under ambient conditions. This was accomplished using an abnormal N-heterocyclic carbene (aNHC)-borane adduct. The intermediate involved in CO2 capture (aNHC-H, HCOO, B(OH)3) was structurally characterized by single-crystal X-ray diffraction. Interestingly, the captured CO2 can be released by heating the intermediate, or by passing this compound through an ion-exchange resin. The capture of CO2 from air can even proceed in the solid state via the formation of a bicarbonate complex (aNHC-H, HCO3, B(OH)3), which was also structurally characterized. A detailed mechanism for this process is proposed based on tandem density functional theory calculations and experiments.
Mc Cusker,Bright
, p. 2093 (1964)
Carbodiimides as catalysts for the reduction of CO2 with boranes
Ramos, Alberto,Anti?olo, Antonio,Carrillo-Hermosilla, Fernando,Fernández-Galán, Rafael,Rodríguez-Diéguez, Antonio,García-Vivó, Daniel
supporting information, p. 4700 - 4703 (2018/05/22)
Carbodiimides catalyse the reduction of CO2 with H-BBN or BH3·SMe2 to give either mixtures of CH2(OBBN)2 and CH3OBBN or (MeOBO)3 and B(OMe)3 under mild conditions (25-60 °C, 1 atm CO2). Stoichiometric reactions and theoretical calculations were performed to unveil the mechanism of these catalytic processes.
