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Title: Supported Single-Site Ti(IV) on a Metal–Organic Framework for the Hydroboration of Carbonyl Compounds

Abstract

Here, a stable and structurally well-defined titanium alkoxide catalyst supported on a metal-organic-framework (MOF) of UiO-67 topology (ANL1-Ti(O iPr) 2) was synthesized and fully characterized by a variety of analytical and spectroscopic techniques, including BET, TGA, PXRD, XAS, DRIFT, SEM, and DFT computations. The Ti-functionalized MOF was demonstrated active for the catalytic hydroboration of a wide range of aldehydes and ketones with HBpin as the boron source. Compared to traditional homogeneous and supported hydroboration catalysts, ANL1-Ti(O iPr) 2 is completely recyclable and reusable, making it a promising hydroboration catalyst alternative for green and sustainable chemical synthesis. DFT calculations suggest that the catalytic hydroboration proceeds via a (1) hydride transfer between the active Ti-hydride species and a carbonyl moiety (rate determining step), and (2) alkoxide transfer (intramolecular σ-bond metathesis) to generate the boronate ester product.

Authors:
 [1];  [1]; ORCiD logo [2]; ORCiD logo [3];  [1];  [4];  [3];  [2]; ORCiD logo [2];  [2]; ORCiD logo [2]; ORCiD logo [1];  [2]; ORCiD logo [2]
  1. Wuhan Univ., Wuhan (People's Republic of China); Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Argonne National Lab. (ANL), Lemont, IL (United States)
  3. Illinois Institute of Technology, Chicago, IL (United States)
  4. Argonne National Lab. (ANL), Lemont, IL (United States); Univ. of Puerto Rico at Cayey, Cayey, Puerto Rico (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1422836
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Organometallics
Additional Journal Information:
Journal Volume: 36; Journal Issue: 20; Journal ID: ISSN 0276-7333
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Huang, Zhiyuan, Liu, Dong, Camacho-Bunquin, Jeffrey, Zhang, Guanghui, Yang, Dali, Lopez-Encarnacion, Juan M., Xu, Yunjie, Ferrandon, Magali S., Niklas, Jens, Poluektov, Oleg G., Jellinek, Julius, Lei, Aiwen, Bunel, Emilio E., and Delferro, Massimiliano. Supported Single-Site Ti(IV) on a Metal–Organic Framework for the Hydroboration of Carbonyl Compounds. United States: N. p., 2017. Web. doi:10.1021/acs.organomet.7b00544.
Huang, Zhiyuan, Liu, Dong, Camacho-Bunquin, Jeffrey, Zhang, Guanghui, Yang, Dali, Lopez-Encarnacion, Juan M., Xu, Yunjie, Ferrandon, Magali S., Niklas, Jens, Poluektov, Oleg G., Jellinek, Julius, Lei, Aiwen, Bunel, Emilio E., & Delferro, Massimiliano. Supported Single-Site Ti(IV) on a Metal–Organic Framework for the Hydroboration of Carbonyl Compounds. United States. doi:10.1021/acs.organomet.7b00544.
Huang, Zhiyuan, Liu, Dong, Camacho-Bunquin, Jeffrey, Zhang, Guanghui, Yang, Dali, Lopez-Encarnacion, Juan M., Xu, Yunjie, Ferrandon, Magali S., Niklas, Jens, Poluektov, Oleg G., Jellinek, Julius, Lei, Aiwen, Bunel, Emilio E., and Delferro, Massimiliano. Thu . "Supported Single-Site Ti(IV) on a Metal–Organic Framework for the Hydroboration of Carbonyl Compounds". United States. doi:10.1021/acs.organomet.7b00544. https://www.osti.gov/servlets/purl/1422836.
@article{osti_1422836,
title = {Supported Single-Site Ti(IV) on a Metal–Organic Framework for the Hydroboration of Carbonyl Compounds},
author = {Huang, Zhiyuan and Liu, Dong and Camacho-Bunquin, Jeffrey and Zhang, Guanghui and Yang, Dali and Lopez-Encarnacion, Juan M. and Xu, Yunjie and Ferrandon, Magali S. and Niklas, Jens and Poluektov, Oleg G. and Jellinek, Julius and Lei, Aiwen and Bunel, Emilio E. and Delferro, Massimiliano},
abstractNote = {Here, a stable and structurally well-defined titanium alkoxide catalyst supported on a metal-organic-framework (MOF) of UiO-67 topology (ANL1-Ti(OiPr)2) was synthesized and fully characterized by a variety of analytical and spectroscopic techniques, including BET, TGA, PXRD, XAS, DRIFT, SEM, and DFT computations. The Ti-functionalized MOF was demonstrated active for the catalytic hydroboration of a wide range of aldehydes and ketones with HBpin as the boron source. Compared to traditional homogeneous and supported hydroboration catalysts, ANL1-Ti(OiPr)2 is completely recyclable and reusable, making it a promising hydroboration catalyst alternative for green and sustainable chemical synthesis. DFT calculations suggest that the catalytic hydroboration proceeds via a (1) hydride transfer between the active Ti-hydride species and a carbonyl moiety (rate determining step), and (2) alkoxide transfer (intramolecular σ-bond metathesis) to generate the boronate ester product.},
doi = {10.1021/acs.organomet.7b00544},
journal = {Organometallics},
number = 20,
volume = 36,
place = {United States},
year = {Thu Oct 12 00:00:00 EDT 2017},
month = {Thu Oct 12 00:00:00 EDT 2017}
}

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