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

ASJC Scopus subject areas

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

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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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AU - Johnson, Samantha I.

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AU - Kaminsky, Werner

AU - Bullock, R. Morris

PY - 2019/1/1

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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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