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

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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.

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

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Publication details

The article was received on 05 Sep 2019, accepted on 21 Oct 2019 and first published on 05 Nov 2019


Article type: Communication
DOI: 10.1039/C9CC06915A
Chem. Commun., 2019, Advance Article

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    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, Advance Article , DOI: 10.1039/C9CC06915A

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