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- Title
On the Redox Reactivity of a Geometrically Constrained Phosphorus(III) Compound.
- Authors
Robinson, Thomas P.; De Rosa, Daniel; Aldridge, Simon; Goicoechea, Jose M.
- Abstract
The reactivity of a geometrically constrained phosphorus(III) complex bearing the N, N-bis(3,5-di- tert-butyl-2-phenolate)amide pincer ligand (P(ONO); 1) towards oxidants and reductants is explored. This compound can be readily oxidized to the phosphorus(V) dihalo-derivatives P(ONO)X2 where X=Cl ( 2), Br ( 3) and I ( 4). Attempts at isolating the analogous difluoride through oxidation of 1 were unsuccessful yielding only the hydrofluoride P(ONO)(H)F ( 5), however P(ONO)F2 ( 6) can be accessed via a halide exchange reaction of 2 with KF. Compound 2 can be employed as a precursor to novel cationic species through chloride ion displacement using strong Lewis bases. Thus, reaction of 2 with two or three molar equivalents of dimethylaminopyridine (DMAP) affords [P(ONO)(Cl)(DMAP)2]+ ( 7) and [P(ONO)(DMAP)3]2+ ( 8). Reaction of 2 with the weaker bidentate base 2,2′-bipyridine (bipy) affords [P(ONO)(Cl)(bipy)]+ ( 9), although this species was only accessible upon addition of a halide abstracting agent. The dicationic tris(pyridine) adduct [P(ONO)(py)3]2+ ( 10) is also accessible by reaction of 4 with pyridine. Oxidation of 1 using oxygen gas proceeds slowly and allows for the observation of two compounds, a mixed valence dimeric phosphorus(III)/phosphorus(V) compound [P(ONO)(μ2-O)(μ2:κ1,κ2-ONO)P] ( 11) and the fully oxidized species [P(ONO)(μ2-O)(μ2:κ1,κ2-ONO)P(O)] ( 12). Finally, reaction of 1 using KC8 results in the dimerization of the putative radical anion [P(ONO)].− through formation of a P−P bond to afford [P(ONO)]22− ( 13). Reactions with TEMPO result in the formation of the trigonal bipyramidal species P(ONO)(TEMPO)2 ( 14).
- Subjects
CHEMICAL reactions; PHOSPHORUS compounds; OXIDATION-reduction reaction; COORDINATION compounds; LIGAND exchange reactions
- Publication
Chemistry - A European Journal, 2017, Vol 23, Issue 61, p15455
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201703119