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Synthesis and EPR/UV/Vis‐NIR Spectroelectrochemical Investigation of a Persistent Phosphanyl Radical Dication
Author(s) -
Schwedtmann Kai,
Schulz Stephen,
Hennersdorf Felix,
Strassner Thomas,
Dmitrieva Evgenia,
Weigand Jan J.
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201502737
Subject(s) - dication , electron paramagnetic resonance , chemistry , protonation , trifluoromethanesulfonate , medicinal chemistry , radical ion , salt (chemistry) , photochemistry , inorganic chemistry , ion , organic chemistry , catalysis , nuclear magnetic resonance , physics
The reaction of the bis(imidazoliumyl)‐substituted P I cation [(2‐Im Dipp )P(4‐Im Dipp )] + ( 10 + ) (2‐Im=imidazolium‐2‐yl; 4‐Im=imidazolium‐4‐yl; Dipp=2,6‐di‐isopropylphenyl) with trifluoromethanesulfonic acid (HOTf) or methyl trifluoromethylsulfonate (MeOTf) yields the corresponding protonated [(2‐Im Dipp )PH(4‐Im Dipp )] 2+ ( 11 2+ ) and methylated [(2‐Im Dipp )PMe(4‐Im Dipp )] 2+ ( 12 2+ ) dications, respectively. EPR/UV/Vis‐NIR spectroelectrochemical investigation of the low‐coordinated P I cation 10 + predicted a stable and “bottleable” P‐centered radical dication [(2‐Im Dipp )P(4‐Im Dipp )] 2+. ( 13 2+. ). The reaction of 10 + with the nitrosyl salt NO[OTf] yields the persistent phosphanyl radical dication 13 2+. as triflate salt in crystalline form. Quantum chemical investigation revealed an exceptional high spin density at the P atom.