Organometallics
Organometallics
5 years ago

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

Supported Single-Site Ti(IV) on a Metal–Organic Framework for the Hydroboration of Carbonyl Compounds
Emilio E. Bunel, Guanghui Zhang, Jeffrey Camacho-Bunquin, Dali Yang, Aiwen Lei, Jens Niklas, Zhiyuan Huang, Juan M. López-Encarnación, Julius Jellinek, Massimiliano Delferro, Oleg G. Poluektov, Magali S. Ferrandon, Dong Liu, Yunjie Xu
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. In addition, ANL1-Ti(OiPr)2 catalyst exhibits remarkable hydroboration selectivity toward aldehydes vs ketone in competitive study. 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 borate ester product.

Publisher URL: http://dx.doi.org/10.1021/acs.organomet.7b00544

DOI: 10.1021/acs.organomet.7b00544

You might also like
Discover & Discuss Important Research

Keeping up-to-date with research can feel impossible, with papers being published faster than you'll ever be able to read them. That's where Researcher comes in: we're simplifying discovery and making important discussions happen. With over 19,000 sources, including peer-reviewed journals, preprints, blogs, universities, podcasts and Live events across 10 research areas, you'll never miss what's important to you. It's like social media, but better. Oh, and we should mention - it's free.

  • Download from Google Play
  • Download from App Store
  • Download from AppInChina

Researcher displays publicly available abstracts and doesn’t host any full article content. If the content is open access, we will direct clicks from the abstracts to the publisher website and display the PDF copy on our platform. Clicks to view the full text will be directed to the publisher website, where only users with subscriptions or access through their institution are able to view the full article.