Triple Hydrogen Atom Abstraction From Mn–NH3 Complexes Results ...

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 NHx 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.

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