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Title: Cooperative H2 Activation across a Metal–Metal Multiple Bond and Hydrogenation Reactions Catalyzed by a Zr/Co Heterobimetallic Complex

Abstract

In the quest for active and selective catalysts featuring nonprecious metals, bimetallic cooperativity poses a unique opportunity to promote catalytic reactions and influence selectivity. While examples of stoichiometric H2 activation across metal–metal bonds have been reported, there have been limited advances toward the incorporation of a well-defined cooperative bimetallic H2 activation process into a catalytic cycle for the hydrogenation of unsaturated hydrocarbons. We demonstrate that facile activation of H2 by two nonprecious metals is facilitated by metal–metal cooperativity in the coordinatively unsaturated Zr/Co bis(phosphinoamide) complexes (THF)(I)Zr(XylNPiPr2)2CoPR3 (3-PMe3 and 3-PMePh2, Xyl =3,5-dimethylphenyl), which feature highly polar Zr–Co triple bonds. Owing to the stabilizing nature of the metal–metal bond, the H2 activation products (THF)(I)Zr(μ-H)(XylNPiPr2)2Co(H)(PR3) (4-PMe3 and 4-PMePh2), which feature one terminally bound Co hydride and one hydride bridging the two metals, have been isolated and crystallographically characterized. The Zr/Co bimetallic complex 3-PMePh2 is an active catalyst for the hydrogenation of alkenes and semihydrogenation of alkynes, and relevant intermediates including 4-PMePh2 and alkene (5) and alkyne (6) adducts have been identified spectroscopically in situ and isolated and characterized through independent synthesis. The alkyne semihydrogenation reaction catalyzed by 3-PMePh2 exhibits high selectivity for alkene over alkane products and generates an unselective distribution of (E)-more » and (Z)-alkenes via direct formation of both stereoisomers. These findings lend insight into the roles that metal–metal bonding and cooperativity play in the activation of small molecules and the promotion and selectivity of subsequent catalytic transformations.« less

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]
  1. Brandeis Univ., Waltham, MA (United States). Dept. of Chemistry
  2. Brandeis Univ., Waltham, MA (United States). Dept. of Chemistry; The Ohio State Univ., Columbus, OH (United States). Dept. of Chemistry and Biochemistry
Publication Date:
Research Org.:
Brandeis Univ., Waltham, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Contributing Org.:
Ohio State University
OSTI Identifier:
1524777
Alternate Identifier(s):
OSTI ID: 1575199
Grant/Contract Number:  
SC0014151
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 9; Journal Issue: 4; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; heterobimetallic; dihydrogen activation; alkyne semihydrogenation; alkene hydrogenation; metal−metal bonds; cooperative reactivity

Citation Formats

Gramigna, Kathryn M., Dickie, Diane A., Foxman, Bruce M., and Thomas, Christine M. Cooperative H2 Activation across a Metal–Metal Multiple Bond and Hydrogenation Reactions Catalyzed by a Zr/Co Heterobimetallic Complex. United States: N. p., 2019. Web. doi:10.1021/acscatal.8b04390.
Gramigna, Kathryn M., Dickie, Diane A., Foxman, Bruce M., & Thomas, Christine M. Cooperative H2 Activation across a Metal–Metal Multiple Bond and Hydrogenation Reactions Catalyzed by a Zr/Co Heterobimetallic Complex. United States. doi:10.1021/acscatal.8b04390.
Gramigna, Kathryn M., Dickie, Diane A., Foxman, Bruce M., and Thomas, Christine M. Fri . "Cooperative H2 Activation across a Metal–Metal Multiple Bond and Hydrogenation Reactions Catalyzed by a Zr/Co Heterobimetallic Complex". United States. doi:10.1021/acscatal.8b04390. https://www.osti.gov/servlets/purl/1524777.
@article{osti_1524777,
title = {Cooperative H2 Activation across a Metal–Metal Multiple Bond and Hydrogenation Reactions Catalyzed by a Zr/Co Heterobimetallic Complex},
author = {Gramigna, Kathryn M. and Dickie, Diane A. and Foxman, Bruce M. and Thomas, Christine M.},
abstractNote = {In the quest for active and selective catalysts featuring nonprecious metals, bimetallic cooperativity poses a unique opportunity to promote catalytic reactions and influence selectivity. While examples of stoichiometric H2 activation across metal–metal bonds have been reported, there have been limited advances toward the incorporation of a well-defined cooperative bimetallic H2 activation process into a catalytic cycle for the hydrogenation of unsaturated hydrocarbons. We demonstrate that facile activation of H2 by two nonprecious metals is facilitated by metal–metal cooperativity in the coordinatively unsaturated Zr/Co bis(phosphinoamide) complexes (THF)(I)Zr(XylNPiPr2)2CoPR3 (3-PMe3 and 3-PMePh2, Xyl =3,5-dimethylphenyl), which feature highly polar Zr–Co triple bonds. Owing to the stabilizing nature of the metal–metal bond, the H2 activation products (THF)(I)Zr(μ-H)(XylNPiPr2)2Co(H)(PR3) (4-PMe3 and 4-PMePh2), which feature one terminally bound Co hydride and one hydride bridging the two metals, have been isolated and crystallographically characterized. The Zr/Co bimetallic complex 3-PMePh2 is an active catalyst for the hydrogenation of alkenes and semihydrogenation of alkynes, and relevant intermediates including 4-PMePh2 and alkene (5) and alkyne (6) adducts have been identified spectroscopically in situ and isolated and characterized through independent synthesis. The alkyne semihydrogenation reaction catalyzed by 3-PMePh2 exhibits high selectivity for alkene over alkane products and generates an unselective distribution of (E)- and (Z)-alkenes via direct formation of both stereoisomers. These findings lend insight into the roles that metal–metal bonding and cooperativity play in the activation of small molecules and the promotion and selectivity of subsequent catalytic transformations.},
doi = {10.1021/acscatal.8b04390},
journal = {ACS Catalysis},
number = 4,
volume = 9,
place = {United States},
year = {2019},
month = {3}
}

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  • DOI: 10.1002/chem.201901424

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  • Cui, Peng; Xiong, Chunyan; Du, Jun
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  • DOI: 10.1039/c9dt04369a

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  • Xin, Xiaoqing; Zhu, Congqing
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  • Cammarota, Ryan C.; Xie, Jing; Burgess, Samantha A.
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