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

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

Pacific Northwest National Laboratory

Research output: Contribution to journal › Article

1 Citation (Scopus)

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.

Original language	English
Pages (from-to)	14058-14061
Number of pages	4
Journal	Chemical Communications
Volume	55
Issue number	93
DOIs	https://doi.org/10.1039/c9cc06915a
Publication status	Published - Jan 1 2019

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ASJC Scopus subject areas

Catalysis
Electronic, Optical and Magnetic Materials
Ceramics and Composites
Chemistry(all)
Surfaces, Coatings and Films
Metals and Alloys
Materials Chemistry

Cite this

Cook, B. J., Johnson, S. I., Chambers, G. M., Kaminsky, W., & Bullock, R. M. (2019). Triple hydrogen atom abstraction from Mn-NH₃ complexes results in cyclophosphazenium cations. Chemical Communications, 55(93), 14058-14061. https://doi.org/10.1039/c9cc06915a

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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.",

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AB - 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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10.1039/c9cc06915a