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Dihydrogen Adduct (Co-H₂) Complexes Displaying H-atom and Hydride Transfer

Deegan, Meaghan M. and Hannoun, Kareem I. and Peters, Jonas C. (2020) Dihydrogen Adduct (Co-H₂) Complexes Displaying H-atom and Hydride Transfer. Angewandte Chemie International Edition . ISSN 1433-7851. (In Press)

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The prototypical reactivity profiles of transition metal dihydrogen complexes (M‐H₂) 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 H₂ activation, namely direct activation through H‐atom or hydride transfer from the σ‐H₂ adducts. To this end, we describe herein the reactivity of an isostructural pair of a neutral S = ½ and an anionic S = 0 Co‐H₂ adduct, both supported by a trisphosphine borane ligand (P₃^B). The thermally stable metalloradical, (P₃^B)Co(H₂), serves as a competent precursor for hydrogen atom transfer to ᵗBu₃ArO·. What is more, its anionic derivative, the dihydrogen complex [(P₃^B)Co(H­₂)]¹⁻, is a competent precursor for hydride transfer to BEt₃, establishing its remarkable hydricity. The latter finding is essentially without precedent among the vast number of M‐H₂ complexes known.

Item Type:Article
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URLURL TypeDescription
Deegan, Meaghan M.0000-0002-7633-2074
Peters, Jonas C.0000-0002-6610-4414
Alternate Title:Dihydrogen Adduct (Co‐H2) Complexes Displaying H‐atom and Hydride Transfer
Additional Information:© 2020 Wiley‐VCH. Accepted manuscript online: 14 August 2020. Manuscript accepted: 04 August 2020. Manuscript received: 16 July 2020. This research was supported by the Department of Energy (DOE-0235032) with additional facilities support provided by the DOW Next Generation Educator Fund and the Beckman Institute at Caltech. We acknowledge Daniel Suess for initial studies of complex [Co](H) and thank Larry Henling for assistance with refinement of crystallographic data.
Funding AgencyGrant Number
Department of Energy (DOE)DOE-0235032
Dow Next Generation Educator FundUNSPECIFIED
Caltech Beckman InstituteUNSPECIFIED
Subject Keywords:dihydrogen complexes; H₂ adducts; H-atom transfer; hydride transfer; metalloradicals
Record Number:CaltechAUTHORS:20200819-121109133
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Official Citation:Peters, J., Deegan, M. and Hannoun, K. (2020), Dihydrogen Adduct (Co‐H2) Complexes Displaying H‐atom and Hydride Transfer. Angew. Chem. Int. Ed.. Accepted Author Manuscript. doi:10.1002/anie.202009814
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:105029
Deposited By: George Porter
Deposited On:19 Aug 2020 19:30
Last Modified:19 Aug 2020 19:31

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