Please use this identifier to cite or link to this item:
Title: Aluminum-hydride-catalyzed hydroboration of carbon dioxide
Authors: Chia, Cher-Chiek
Teo, Yeow-Chuan
Cham, Ning
Ho, Samuel Ying-Fu
Ng, Zhe-Hua
Toh, Hui-Min
Mézailles, Nicolas
So, Cheuk-Wai
Keywords: Science::Chemistry
Issue Date: 2021
Source: Chia, C., Teo, Y., Cham, N., Ho, S. Y., Ng, Z., Toh, H., Mézailles, N. & So, C. (2021). Aluminum-hydride-catalyzed hydroboration of carbon dioxide. Inorganic Chemistry, 60(7), 4569-4577.
Project: NRF2018-NRF-ANR026 Si-POP 
MOE2019-T2- 2-129 
RG 17/17 
Journal: Inorganic Chemistry 
Abstract: This study describes the first use of a bis(phosphoranyl)methanido aluminum hydride, [ClC(PPh2NMes)2AlH2] (2, Mes = Me3C6H2), for the catalytic hydroboration of CO2. Complex 2 was synthesized by the reaction of a lithium carbenoid [Li(Cl)C(PPh2NMes)2] with 2 equiv of AlH3·NEtMe2 in toluene at -78 °C. 2 (10 mol %) was able to catalyze the reduction of CO2 with HBpin in C6D6 at 110 °C for 2 days to afford a mixture of methoxyborane [MeOBpin] (3a; yield: 78%, TOF: 0.16 h-1) and bis(boryl)oxide [pinBOBpin] (3b). When more potent [BH3·SMe2] was used instead of HBpin, the catalytic reaction was extremely pure, resulting in the formation of trimethyl borate [B(OMe)3] (3e) [catalytic loading: 1 mol % (10 mol %); reaction time: 60 min (5 min); yield: 97.6% (>99%); TOF: 292.8 h-1 (356.4 h-1)] and B2O3 (3f). Mechanistic studies show that the Al-H bond in complex 2 activated CO2 to form [ClC(PPh2NMes)2Al(H){OC(O)H}] (4), which was subsequently reacted with BH3·SMe2 to form 3e and 3f, along with the regeneration of complex 2. Complex 2 also shows good catalytic activity toward the hydroboration of carbonyl, nitrile, and alkyne derivatives.
ISSN: 0020-1669
DOI: 10.1021/acs.inorgchem.0c03507
Schools: School of Physical and Mathematical Sciences 
Rights: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see
Fulltext Permission: open
Fulltext Availability: With Fulltext
Appears in Collections:SPMS Journal Articles

Files in This Item:
File Description SizeFormat 
Manuscript_AlH CO2 catalysis_revised_final.pdf833.44 kBAdobe PDFThumbnail

Citations 20

Updated on Sep 22, 2023

Web of ScienceTM
Citations 20

Updated on Sep 28, 2023

Page view(s)

Updated on Sep 30, 2023

Download(s) 50

Updated on Sep 30, 2023

Google ScholarTM




Items in DR-NTU are protected by copyright, with all rights reserved, unless otherwise indicated.