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Title: Metal–organic layers stabilize earth-abundant metal–terpyridine diradical complexes for catalytic C–H activation

Abstract

Metal–organic layers stabilize Fe II or Co II -terpyridine diradical complexes to catalyze alkylazide C sp3 –H amination and benzylic C–H borylation, respectively.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [2];  [3]; ORCiD logo [2]; ORCiD logo [4]
  1. Department of Chemistry, University of Chicago, Chicago, USA
  2. Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University
  3. Research Computing Center, University of North Carolina, USA
  4. Department of Chemistry, University of Chicago, Chicago, USA, Collaborative Innovation Center of Chemistry for Energy Materials
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1408785
Grant/Contract Number:
AC02-06CH11357
Resource Type:
Journal Article: Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Related Information: CHORUS Timestamp: 2017-12-20 07:17:00; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English

Citation Formats

Lin, Zekai, Thacker, Nathan C., Sawano, Takahiro, Drake, Tasha, Ji, Pengfei, Lan, Guangxu, Cao, Lingyun, Liu, Shubin, Wang, Cheng, and Lin, Wenbin. Metal–organic layers stabilize earth-abundant metal–terpyridine diradical complexes for catalytic C–H activation. United Kingdom: N. p., 2018. Web. doi:10.1039/C7SC03537C.
Lin, Zekai, Thacker, Nathan C., Sawano, Takahiro, Drake, Tasha, Ji, Pengfei, Lan, Guangxu, Cao, Lingyun, Liu, Shubin, Wang, Cheng, & Lin, Wenbin. Metal–organic layers stabilize earth-abundant metal–terpyridine diradical complexes for catalytic C–H activation. United Kingdom. doi:10.1039/C7SC03537C.
Lin, Zekai, Thacker, Nathan C., Sawano, Takahiro, Drake, Tasha, Ji, Pengfei, Lan, Guangxu, Cao, Lingyun, Liu, Shubin, Wang, Cheng, and Lin, Wenbin. 2018. "Metal–organic layers stabilize earth-abundant metal–terpyridine diradical complexes for catalytic C–H activation". United Kingdom. doi:10.1039/C7SC03537C.
@article{osti_1408785,
title = {Metal–organic layers stabilize earth-abundant metal–terpyridine diradical complexes for catalytic C–H activation},
author = {Lin, Zekai and Thacker, Nathan C. and Sawano, Takahiro and Drake, Tasha and Ji, Pengfei and Lan, Guangxu and Cao, Lingyun and Liu, Shubin and Wang, Cheng and Lin, Wenbin},
abstractNote = {Metal–organic layers stabilize Fe II or Co II -terpyridine diradical complexes to catalyze alkylazide C sp3 –H amination and benzylic C–H borylation, respectively.},
doi = {10.1039/C7SC03537C},
journal = {Chemical Science},
number = 1,
volume = 9,
place = {United Kingdom},
year = 2018,
month = 1
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1039/C7SC03537C

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  • Metal–organic layers stabilize Fe IIor Co II-terpyridine diradical complexes to catalyze alkylazide C sp3–H amination and benzylic C–H borylation, respectively.
  • Mono(phosphine)–M (M–PR3; M = Rh and Ir) complexes selectively prepared by postsynthetic metalation of a porous triarylphosphine-based metal–organic framework (MOF) exhibited excellent activity in the hydrosilylation of ketones and alkenes, the hydrogenation of alkenes, and the C–H borylation of arenes. The recyclable and reusable MOF catalysts significantly outperformed their homogeneous counterparts, presumably via stabilizing M–PR3 intermediates by preventing deleterious disproportionation reactions/ligand exchanges in the catalytic cycles.
  • We have designed a strategy for postsynthesis installation of the β-diketiminate (NacNac) functionality in a metal–organic framework (MOF) of UiO-topology. Metalation of the NacNac-MOF (I) with earth-abundant metal salts afforded the desired MOF-supported NacNac-M complexes (M = Fe, Cu, and Co) with coordination environments established by detailed EXAFS studies. The NacNac-Fe-MOF catalyst, I•Fe(Me), efficiently catalyzed the challenging intramolecular sp 3 C–H amination of a series of alkyl azides to afford α-substituted pyrrolidines. The NacNac-Cu-MOF catalyst, I•Cu(THF), was effective in promoting the intermolecular sp 3 C–H amination of cyclohexene using unprotected anilines to provide access to secondary amines in excellent selectivity.more » Finally, the NacNac-Co-MOF catalyst, I•Co(H), was used to catalyze alkene hydrogenation with turnover numbers (TONs) as high as 700 000. All of the NacNac-M-MOF catalysts were more effective than their analogous homogeneous catalysts and could be recycled and reused without a noticeable decrease in yield. The NacNac-MOFs thus provide a novel platform for engineering recyclable earth-abundant-element-based single-site solid catalysts for many important organic transformations.« less
  • Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturatedmore » metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.« less