Triorganoarsenic(V) compounds with internally functionalized oximes: synthetic and spectroscopic aspects of [R3As(Cl)L], [R3As(OH)L] and [R3AsL2]: crystal and molecular structure of [Pr3iAsOH]+Cl−

Triorganoarsenic(V) oximates of the type [R3As{ONC(Me)Ar}2] (1) (R=Pri, Bui; Ar=C5H4N-2, C4H3O-2) are formed by the reactions of R3AsCl2 with the sodium salts of internally functionalized oximes in 1:2 molar ratio in anhydrous benzene. The redistribution products [R3As(X){ONC(Me)Ar}] (2) (X=Cl, Br, OH) are obtained by treatment of 1 with equimolar R3AsX2. [Pr3iAs(OH){ONC(Me)C5H4N-2}] may also be obtained by the reaction of Pr3iAs(OH)2 with the corresponding oxime in 1:1 molar ratio. All of these complexes are characterized by IR and NMR (1H and 13C) spectroscopy and elemental analyses. Controlled hydrolysis of a representative monochloro-complex [Pr3iAs(Cl){ONC(Me)C4H3O-2}] yields crystals of Pr3iAs(OH)Cl in which single crystal X-ray diffraction indicates that there is a distorted tetrahedral environment around arsenic.