Abstract

Tris(2,6-dimethoxyphenyl)arsine and tris(2,6-dimethoxyphenyl)stibine ( Φ 3M( Φ = 2,6-(MeO) 2C 6H 3; M = As an Sb)) reacted with common alkyl halides (RX) to give [Φ 3M-R]X, while Φ 3Bi was unreactive in benzene, or it decomposed in hot alcohols. The reactions of Φ 3M (As, Sb) with butyl bromide in acetonitrile were much faster than that of triphenylphosphine. Treatments of Φ 3M (P, As, Sb)with N-bromosuccinimide (NBS) gave [Φ 3M−OH]Br, while Φ 3Bi decomposed to give 1-bromo-2,6-dimethoxybenzene. [Φ 3M-OH]Br are soluble in water, and the acidity decreased in the order M = P > As > Sb. Treatments of Φ 3M(As, Sb) with aqueous hydrogen peroxide gave the oxides as hydrates, φ 3MO. xH 2O ( x = 1, for M = As and x = 3 for M = Sb), while Φ 3Bi was unreactive or decomposed. Φ 3PO was brominated by NBS to give Φ 3'PO.H 2O ( Φ = 3-Br-2,6-(MeO) 2C 6H 2), which did not react with perchloric acid. In contrast, Φ 3MO. xH 2O (P, As, Sb) reacted with the acid to form the stable hydroxyonium salts [Φ 3M−OH]ClO 4. [Γ 3POH]ClO 4 formed crystals of stable 1 : 1 adducts with a variety of amines. [Φ 3AsOH]ClO 4 formed 1 : 1 adducts when treated with excess amounts of several amines (triethylamine, diethylamine, isobutylamine and piperidine), but they were unstable to leave amines by recrystallization. [Φ 3 SbOH]ClO 4 formed unstable adducts with these amines, or it did not form. [Φ 3PSH]ClO 4 formed 1 : 1 adducts with several amines, or it was deprotonated to give Φ 3MO. xH 2O (P,As) reacted with common RX (X - Br or I) to give [Φ 3M-OR]X, but but φ 3SbO. 3H 2O reacted to give Φ 3SbOH]X. [Φ 3POR]X decomposed reversibly to give Φ 3PO in solutions, although [Φ 3MOR]ClO 4 (P, As) could be recrystallized.

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