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 › peer-review

4 Citations (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 - 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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@article{d0702a0ed93b47efb5e848f6579a9409,

title = "Triple hydrogen atom abstraction from Mn-NH3 complexes results in cyclophosphazenium cations",

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.",

author = "Cook, {Brian J.} and Johnson, {Samantha I.} and Chambers, {Geoffrey M.} and Werner Kaminsky and Bullock, {R. Morris}",

note = "Funding Information: This work was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory (PNNL) is operated by Battelle for the U.S. Department of Energy. Calculations were performed using the Cascade supercomputer at EMSL, a national scientific user facility sponsored by the DOE{\textquoteright}s Office of Biological and Environmental Research and located at PNNL. We thank Dr Benjamin Neisen (PNNL) for collecting X-ray diffraction data on 2, Dr Eric Wiedner, Dr Aaron Appel, Dr Peter Dunn and Dr Spencer Heins (PNNL) for insightful discussions and helpful technical expertise. Publisher Copyright: This journal is {\textcopyright} The Royal Society of Chemistry.",

year = "2019",

doi = "10.1039/c9cc06915a",

language = "English",

volume = "55",

pages = "14058--14061",

journal = "Chemical Communications",

issn = "1359-7345",

publisher = "Royal Society of Chemistry",

number = "93",

}

TY - JOUR

T1 - Triple hydrogen atom abstraction from Mn-NH3 complexes results in cyclophosphazenium cations

AU - Cook, Brian J.

AU - Johnson, Samantha I.

AU - Chambers, Geoffrey M.

AU - Kaminsky, Werner

AU - Bullock, R. Morris

N1 - Funding Information: This work was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory (PNNL) is operated by Battelle for the U.S. Department of Energy. Calculations were performed using the Cascade supercomputer at EMSL, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at PNNL. We thank Dr Benjamin Neisen (PNNL) for collecting X-ray diffraction data on 2, Dr Eric Wiedner, Dr Aaron Appel, Dr Peter Dunn and Dr Spencer Heins (PNNL) for insightful discussions and helpful technical expertise. Publisher Copyright: This journal is © The Royal Society of Chemistry.

PY - 2019

Y1 - 2019

N2 - 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.

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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U2 - 10.1039/c9cc06915a

DO - 10.1039/c9cc06915a

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C2 - 31691686

AN - SCOPUS:85075228326

VL - 55

SP - 14058

EP - 14061

JO - Chemical Communications

JF - Chemical Communications

SN - 1359-7345

IS - 93