Dihydrogen Adduct (Co–H2) Complexes Displaying H–Atom and Hydride Transfer
Abstract
Abstract The prototypical reactivity profiles of transition metal dihydrogen complexes (M‐H 2 ) are well‐characterized with respect to oxidative addition (to afford dihydrides, M(H) 2 ) and as acids, heterolytically delivering H + to a base and H − to the metal. In the course of this study we explored plausible alternative pathways for H 2 activation, namely direct activation through H‐atom or hydride transfer from the σ‐H 2 adducts. To this end, we describe herein the reactivity of an isostructural pair of a neutral S = and an anionic S =0 Co‐H 2 adduct, both supported by a trisphosphine borane ligand (P 3 B ). The thermally stable metalloradical, (P 3 B )Co(H 2 ), serves as a competent precursor for hydrogen atom transfer to t Bu 3 ArO ⋅ . What is more, its anionic derivative, the dihydrogen complex [(P 3 B )Co(H 2 )] 1− , is a competent precursor for hydride transfer to BEt 3 , establishing its remarkable hydricity. The latter finding is essentially without precedent among the vast number of M‐H 2 complexes known.
- Publication Date:
- Research Org.:
- California Institute of Technology (CalTech), Pasadena, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1707685
- Alternate Identifier(s):
- OSTI ID: 1786200
- Grant/Contract Number:
- SC0019136; 0235032
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition); Journal Volume: 59; Journal Issue: 50; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Deegan, Meaghan M., Hannoun, Kareem I., and Peters, Jonas C. Dihydrogen Adduct (Co–H2) Complexes Displaying H–Atom and Hydride Transfer. United States: N. p., 2020.
Web. doi:10.1002/anie.202009814.
Deegan, Meaghan M., Hannoun, Kareem I., & Peters, Jonas C. Dihydrogen Adduct (Co–H2) Complexes Displaying H–Atom and Hydride Transfer. United States. https://doi.org/10.1002/anie.202009814
Deegan, Meaghan M., Hannoun, Kareem I., and Peters, Jonas C. Fri .
"Dihydrogen Adduct (Co–H2) Complexes Displaying H–Atom and Hydride Transfer". United States. https://doi.org/10.1002/anie.202009814. https://www.osti.gov/servlets/purl/1707685.
@article{osti_1707685,
title = {Dihydrogen Adduct (Co–H2) Complexes Displaying H–Atom and Hydride Transfer},
author = {Deegan, Meaghan M. and Hannoun, Kareem I. and Peters, Jonas C.},
abstractNote = {Abstract The prototypical reactivity profiles of transition metal dihydrogen complexes (M‐H 2 ) are well‐characterized with respect to oxidative addition (to afford dihydrides, M(H) 2 ) and as acids, heterolytically delivering H + to a base and H − to the metal. In the course of this study we explored plausible alternative pathways for H 2 activation, namely direct activation through H‐atom or hydride transfer from the σ‐H 2 adducts. To this end, we describe herein the reactivity of an isostructural pair of a neutral S = and an anionic S =0 Co‐H 2 adduct, both supported by a trisphosphine borane ligand (P 3 B ). The thermally stable metalloradical, (P 3 B )Co(H 2 ), serves as a competent precursor for hydrogen atom transfer to t Bu 3 ArO ⋅ . What is more, its anionic derivative, the dihydrogen complex [(P 3 B )Co(H 2 )] 1− , is a competent precursor for hydride transfer to BEt 3 , establishing its remarkable hydricity. The latter finding is essentially without precedent among the vast number of M‐H 2 complexes known.},
doi = {10.1002/anie.202009814},
journal = {Angewandte Chemie (International Edition)},
number = 50,
volume = 59,
place = {United States},
year = {Fri Aug 14 00:00:00 EDT 2020},
month = {Fri Aug 14 00:00:00 EDT 2020}
}
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