skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Abstract

ABSTRACT: 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.

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. College of Chemistry &, Molecular Sciences, Institute of Advanced Studies, Wuhan University, Wuhan 430072, PR China; Chemical Sciences &, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
  2. Chemical Sciences &, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
  3. Department of Biological and Chemical Sciences, Illinois Institute of Technology, Chicago, Illinois 60616, United States
  4. Chemical Sciences &, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Department of Mathematics-Physics, University of Puerto Rico at Cayey, Cayey, Puerto Rico 00736, 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
DOE Contract Number:
AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: Organometallics; Journal Volume: 36; Journal Issue: 20
Country of Publication:
United States
Language:
English

Citation Formats

Huang, Zhiyuan, Liu, Dong, Camacho-Bunquin, Jeffrey, Zhang, Guanghui, Yang, Dali, López-Encarnación, 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, López-Encarnación, 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, López-Encarnación, Juan M., Xu, Yunjie, Ferrandon, Magali S., Niklas, Jens, Poluektov, Oleg G., Jellinek, Julius, Lei, Aiwen, Bunel, Emilio E., and Delferro, Massimiliano. Tue . "Supported Single-Site Ti(IV) on a Metal–Organic Framework for the Hydroboration of Carbonyl Compounds". United States. doi:10.1021/acs.organomet.7b00544.
@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 López-Encarnación, 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 = {ABSTRACT: 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 = {Tue Oct 10 00:00:00 EDT 2017},
month = {Tue Oct 10 00:00:00 EDT 2017}
}