Triple Hydrogen Atom Abstraction from Mn-NH3 Complexes Results in Cyclophosphazenium Cations

Cook, Brian J.; Johnson, Samantha JI; Chambers, Geoffrey M.; Kaminsky, Werner; Bullock, Ronald M.

doi:10.1039/C9CC06915A

Triple Hydrogen Atom Abstraction from Mn-NH3 Complexes Results in Cyclophosphazenium Cations

Journal Article · Tue Dec 03 23:00:00 EST 2019 · Chemical Communications

DOI:https://doi.org/10.1039/C9CC06915A· OSTI ID:1614923

Cook, Brian J. ^[1]; Johnson, Samantha JI ^[1]; ^[1]; Kaminsky, Werner ^[2]; ^[1]

BATTELLE (PACIFIC NW LAB)
University of Washington

All three hydrogen atoms of the NH3 ligand of [Mn(depe)2(CO)(NH3)]+ are abstracted in reactions with 2,4,6-tri-tert-butylphenoxyl radical, resulting in the isolation of a rare cyclophosphazenium cation [(Et2P(CH2)2PEt2)N]+, in 76% yield. Similar reactions are observed for [Mn(dppe)2(CO)(NH3)]+. Computational studies suggest that insertion of NH into a Mn-P bond provides a strong thermodynamic driving force. Contextualization of this surprising reaction in the paucity of NH3 oxidation by molecular complexes provides insights on catalyst design and breaking strong N-H bonds.

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1614923

Report Number(s):: PNNL-SA-144932

Journal Information:: Chemical Communications, Journal Name: Chemical Communications Journal Issue: 93 Vol. 55

Country of Publication:: United States

Language:: English

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