Stable and persistent phosphorus radicals are phosphorus-centred radicals that are isolable and can exist for at least short periods of time. Radicals consisting of main group elements are often very reactive and undergo uncontrollable reactions, notably dimerization and polymerization. The common strategies for stabilising these phosphorus radicals usually include the delocalisation of the unpaired electron over a pi system or nearby electronegative atoms, and kinetic stabilisation with bulky ligands. Stable and persistent phosphorus radicals can be classified into three categories: neutral, cationic, and anionic radicals. Each of these classes involve various sub-classes, with neutral phosphorus radicals being the most extensively studied. Phosphorus exists as one isotope 31P (I = 1/2) with large hyperfine couplings relative to other spin active nuclei, making phosphorus radicals particularly attractive for spin-labelling experiments.
Neutral phosphorus radicals
Neutral phosphorus radicals include a large range of conformations with varying spin densities at the phosphorus. Generally, they can categorised as mono- and bi/di-radicals (also referred to as bisradicals and biradicaloids) for species containing one or two radical phosphorus centres respectively.
Monoradicals
In 1966, Muller et. al published the first electron paramagnetic resonance (EPR/ESR) spectra displaying evidence for the existence of phosphorus-containing radicals. Since then a variety of phosphorus monoradicals have been synthesised and isolated. Common ones include phosphinyl (R2P•), phosphonyl (R2PO•), and phosphoranyl (R4P•) radicals.
Synthesis
Synthetic methods for obtaining neutral phosphorus mondoradicals include photolytic reduction of trivalent phosphorus chlorides, P-P homolytic cleavage, single electron oxidation of phosphines, and cleavage of P-S or P-Se bonds.
The first persistent two-coordinate phosphorus-centred radicals [(Me3Si)2N]2P• and [(Me3Si)2CH]2P• were reported in 1976 by Lappert and co-workers. They are prepared by photolysis of the corresponding three-coordinate phosphorus chlorides in toluene in the presence of an electron-rich olifin. In 2000, the Power group found that this species can be synthesised from the dissolution, melting or evaporation of the dimer.
In 2001, Grützmacher et al. reported the first stable diphosphanyl radical [Mes*MeP-PMes*]• (Mes = 1,3,5-trimethylbenzene) from the reduction of the phosphonium salt [Mes*MeP-PMes*]+(O3SCF3)− in an acetonitrile solution containing tetrakis(dimethylamino)ethylene (TDE) at room temperature, yielding yellow crystals. The monomer is stable below -30 ºC in the solid state for a few days. At room temperature the species decomposes in solution and in the solid state with a half life of 30 minutes at 3 x 10−2 M.
The first structurally characterised phosphorus radical [Me3SiNP(µ3-NtBu)3{ µ3-Li(thf)}3X]• (X = Br, I) was synthesised by Armstrong et al. in 2004 by the oxidation of the starting material with halogens bromide or iodine in a mixture of toluene and THF at 297 K. This produces blue crystals that can be characterised by X-ray crystallography. The steric bulk of the alkyl-imido groups was identified as playing a major role in the stabilising of these radicals.
In 2006, Ito et al. prepared an air tolerant and thermally stable 1,3-diphosphayclobutenyl radical. Sterically bulky phospholkyne (Mes*C≡P) is treated with 0.5 equiv of t-BuLi in THF to form a 1,3 diphosphaalkyl anion. This is reduced with iodine solution to form a red product. The species is a planar four-membered diphosphacyclobutane (C2P2) ring with the Mes* having torsional angles with the C2P2 plane.
Metal stabilised radicals
In 2007, Cummins et al. synthsised a phosphorus radical using nitridovanadium trisanilide metallo-ligands with similar form to Lappert, Power and co-workers' "jack-in-the-box" diphosphines. This is made by the synthesis of the radical precursor ClP[NV{ N(Np)Ar}]3]2 followed by its one electron reduction with Ti[N(tBu)Ar]3 or potassium graphite to yield dark brown crystals in 77% yield. EPR data showed delocalisation of electron spin across the two 51V and one 31P nuclei. This was consistent with computation, supporting the reported resonance structures. This delocalisation across the vanadium atoms was identified as the source of stabilisation for this species due to the ease for transition metals to undergo one-electron chemistry. Cummins and co-workers postulated that the p-character of the system could be tuned by changing the metal centres.
Other metals stabilised radicals have been reported by Scheer et al, and Schneider et al using ligand containing tungsten and osmium respectively.