Phosphoranimines containing cationic N-imidazolinium moieties

Klaehn, John R.; Rollins, Harry W.; McNally, Joshua S.; Arulsamy, Navamoney; Dufek, Eric J.

doi:10.1016/j.ica.2017.05.075

Title: Phosphoranimines containing cationic N-imidazolinium moieties

Journal Article · 31 August 2017 · Inorganica Chimica Acta

DOI: https://doi.org/10.1016/j.ica.2017.05.075 · OSTI ID:1470975

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^[1]; Arulsamy, Navamoney ^[2];

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Idaho National Lab. (INL), Idaho Falls, ID (United States). Biological and Chemical Processing
Univ. of Wyoming, Laramie, WY (United States). Dept. of Chemistry
Idaho National Lab. (INL), Idaho Falls, ID (United States). Energy Storage and Advanced Vehicles

For this study, three new monomeric phosphoranimines (PAs; R'—N=PR₃) were synthesized by the Staudinger route using 2-azido-1,3-dimethylimidazolinium hexafluorophosphate [ADMImPF] and various phosphines to form their respective PA salts of triphenylphosphine (1), tri(n-octyl)phosphine (2), and tris(2,2,2-trifluoroethoxy)phosphite (3). These PA salts have a cationic imidazolinium moiety attached to nitrogen. Interestingly, 2 is a room temperature ionic liquid (RTIL) with a melting point around -5°C and a viscosity of 740cP at 25.5°C. 1 and 2 show stability to moisture exposure and atmosphere for weeks whereas 3 is not stable toward atmospheric moisture undergoing decomposition to form 2-amino-1,3-dimethylimidazolinium phosphate (4). Thermal analyses reveal that 1 and 2 are stable to 90°C under nitrogen, but 3 undergoes degradation by exposure to moisture and/or elevated temperature. All compounds exhibit similar multinuclear NMR chemical shifts as compared to their corresponding phosphine oxide counterparts. However, their respective X-ray structure determinations indicate that 2 has an open structure with the octyl groups that avoid the ionic charges, whereas 1 and 3 have tighter structural packing of the hexafluorophosphate to their pendant groups.$$\longequal$$

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Research Organization:: Idaho National Laboratory (INL), Idaho Falls, ID (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE); USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: AC07-05ID14517

OSTI ID:: 1470975

Alternate ID(s):: OSTI ID: 1550295

Report Number(s):: INL/JOU-16-40779-Rev000

Journal Information:: Inorganica Chimica Acta, Journal Name: Inorganica Chimica Acta Journal Issue: C Vol. 466; ISSN 0020-1693

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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CCDC 1543768: Experimental Crystal Structure Determination: QEBXON : 1,3-dimethyl-2-[(triphenyl-λ5-phosphanylidene)amino]-4,5-dihydro-1H-imidazol-3-ium hexafluorophosphate Space Group: P 21/c (14), Cell: a 10.2614(2)Å b 17.1198(3)Å c 14.2207(3)Å, α 90° β 108.6855(10)° γ 90° Klaehn, John; Rollins, Harry; McNally, Joshua https://doi.org/10.5517/ccdc.csd.cc1ntdzv The current record is supplemented by this dataset	dataset	April 2017
CCDC 1543765: Experimental Crystal Structure Determination: QEBXAZ : 2-amino-1,3-dimethyl-4,5-dihydro-1H-imidazol-3-ium hexafluorophosphate Klaehn, John; Rollins, Harry; McNally, Joshua https://doi.org/10.5517/ccdc.csd.cc1ntdwr The current record is supplemented by this dataset	dataset	April 2017
CCDC 1543767: Experimental Crystal Structure Determination: QEBXIH : 1,3-dimethyl-2-{[tris(2,2,2-trifluoroethoxy)-λ5-phosphanylidene]amino}-4,5-dihydro-1H-imidazol-3-ium hexafluorophosphate Klaehn, John; Rollins, Harry; McNally, Joshua https://doi.org/10.5517/ccdc.csd.cc1ntdyt The current record is supplemented by this dataset	dataset	April 2017
CCDC 1543766: Experimental Crystal Structure Determination: QEBXED : 1,3-dimethyl-2-[(trioctyl-λ5-phosphanylidene)amino]-4,5-dihydro-1H-imidazol-3-ium hexafluorophosphate Klaehn, John; Rollins, Harry; McNally, Joshua https://doi.org/10.5517/ccdc.csd.cc1ntdxs The current record is supplemented by this dataset	dataset	April 2017

Title: Phosphoranimines containing cationic N-imidazolinium moieties

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References (40)

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