Synthesis and Redox Properties of (3-Phenothiazinomesityl)- and (4-Phenothiazinoduryl)dimesitylphosphines and the Corresponding Arsines

Abstract

To construct the novel redox systems possessing the trimesitylphosphine- or trimesitylarsine-type substructure as a reversible redox site, dimesityl(3-phenothiazinomesityl)phosphine, dimesityl(4-phenothiazinoduryl)phosphine, and the corresponding arsines were synthesized (mesityl = 2,4,6-trimethylphenyl, duryl = 2,3,5,6-tetramethylphenyl). The key synthetic intermediates, (3-bromomesityl)dimesitylphosphine, (4-bromoduryl)dimesitylphosphine, and the analogous arsines were prepared by successive addition of the corresponding Grignard reagents to phosphorus or arsenic trichloride. The (bromoaryl)phosphines and -arsines were converted to the corresponding (iodoaryl)phosphines and -arsines and coupled with phenothiazine in the presence of copper to afford the phenothiazinophosphino- and phenothiazinoarsinobenzenes. The cyclic voltammograms of the phenothiazinopnictogenobenzenes thus obtained exhibit two-step redox waves corresponding to oxidation on the pnictogen as well as phenothiazine redox centers. The phenothiazino group contributes to stability of the redox systems, and the phenothiazinophosphinobenzenes display two-step nearly reversible redox waves at −78 °C. On the other hand, the cyclic voltammograms of the phenothiazinoarsinobenzenes consist of the first reversible wave followed by the second irreversible wave, suggesting decomposition at the unstable arsenic redox center. The pnictogen redox centers of the phenothiazinopnictogenobenzenes are unstable as compared with those of the corresponding trimesityl derivatives. Chemical oxidation of the phenothiazinophosphinobenzenes and phenothiazinoarsinobenzenes by tris(4-bromophenyl)aminium perchlorate, which can oxidize trimesitylphosphine and trimesitylarsine to the corresponding cation radicals, was studied by EPR. However, only the nitrogen-centered cation radical was observed probably because of the instability of the phosphorus as well as arsenic radical centers.