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
M3 - Article
C2 - 31691686
AN - SCOPUS:85075228326
VL - 55
SP - 14058
EP - 14061
JO - Chemical Communications
JF - Chemical Communications
SN - 1359-7345
IS - 93
ER -