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Controlled Redox Chemistry at Cerium within a Tripodal Nitroxide Ligand Framework
Author(s) -
Bogart Justin A.,
Lippincott Connor A.,
Carroll Patrick J.,
Booth Corwin H.,
Schelter Eric J.
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201502952
Subject(s) - cerium , redox , nitroxide mediated radical polymerization , chemistry , ligand (biochemistry) , photochemistry , inorganic chemistry , organic chemistry , polymerization , biochemistry , polymer , receptor , radical polymerization
Ligand reorganization has been shown to have a profound effect on the outcome of cerium redox chemistry. Through the use of a tethered, tripodal, trianionic nitroxide ligand, [((2‐ t BuNOH)C 6 H 4 CH 2 ) 3 N] 3− (TriNO x 3− ), controlled redox chemistry at cerium was accomplished, and typically reactive complexes of tetravalent cerium were isolated. These included rare cationic complexes [Ce(TriNO x )thf][BAr F 4 ], in which Ar F =3,5‐(CF 3 ) 2 ‐C 6 H 3 , and [Ce(TriNO x )py][OTf]. A rare complete Ce–halide series, Ce(TriNO x )X, in which X=F − , Cl − , Br − , I − , was also synthesized. The solution chemistry of these complexes was explored through detailed solution‐phase electrochemistry and 1 H NMR experiments and showed a unique shift in the ratio of species with inner‐ and outer‐sphere anions with size of the anionic X − group. DFT calculations on the series of calculations corroborated the experimental findings.