Triple hydrogen atom abstraction from Mn–NH3 complexes results in cyclophosphazenium cations

Brian J. Cook; Samantha I. Johnson; Geoffrey M. Chambers; Werner Kaminsky; R. Morris Bullock

doi:10.1039/C9CC06915A

You do not have JavaScript enabled. Please enable JavaScript to access the full features of the site or access our non-JavaScript page.

Triple hydrogen atom abstraction from Mn–NH₃ complexes results in cyclophosphazenium cations†

Brian J. Cook,^a Samantha I. Johnson,

^a Geoffrey M. Chambers,^a Werner Kaminsky

^b and R. Morris Bullock

*^a

Author affiliations

* Corresponding authors

^a Center for Molecular Electrocatalysis, Pacific Northwest National Laboratory P.O. Box 999, Richland, WA 99352, USA
E-mail: morris.bullock@pnnl.gov

^b Department of Chemistry, University of Washington, Box 951700, Seattle, WA 98195, USA

Abstract

All hydrogen atoms of the NH₃ in [Mn(depe)₂(CO)(NH₃)]⁺ are abstracted by 2,4,6-tri-tert-butylphenoxyl radical, resulting in the isolation of a rare cyclophosphazenium cation, [(Et₂P(CH₂)₂PEt₂)N]⁺, in 76% yield. An analogous reaction is observed for [Mn(dppe)₂(CO)(NH₃)]⁺. Computations suggest insertion of NH_x into a Mn–P bond provides the thermodynamic driving force. Contextualization of this reaction provides insights on catalyst design and breaking strong N–H bonds.

Download options Please wait...

Supplementary files

Article information

DOI: https://doi.org/10.1039/C9CC06915A
Article type: Communication
Submitted: 05 Sep 2019
Accepted: 21 Oct 2019
First published: 05 Nov 2019

Download Citation

Chem. Commun., 2019,55, 14058-14061

Author version available

Download author version (PDF)

Permissions

Request permissions

Triple hydrogen atom abstraction from Mn–NH₃ complexes results in cyclophosphazenium cations

B. J. Cook, S. I. Johnson, G. M. Chambers, W. Kaminsky and R. M. Bullock, Chem. Commun., 2019, 55, 14058 DOI: 10.1039/C9CC06915A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Social activity

Fetching data from CrossRef.
This may take some time to load.

Chemical Communications