Hypervalent organobismuth(iii) carbonate, chalcogenides and halides with the pendant arm ligands 2-(Me2NCH2)C6H4 and 2,6-(Me2NCH2)2C6H3

Abstract

R₂BiOH (1) [R = 2-(Me₂NCH₂)C₆H₄] and (R₂Bi)₂O (2) are formed by hydrolysis of R₂BiCl with KOH. Single crystals of 2 were obtained by air oxidation of (R₂Bi)₂. The reaction of R₂BiCl and Na₂CO₃ leads to (R₂Bi)₂CO₃ (3). 3 is also formed by the absorption of CO₂ from the air in solutions of 1 or 2 in diethyl ether or toluene. (R₂Bi)₂S (4) is obtained from R₂BiCl and Na₂S or from (R₂Bi)₂ and S₈. Exchange reactions between R₂BiCl and KBr or NaI give R₂BiX [X = Br (5), I (6)]. The reaction of RBiCl₂ (7) with Na₂S and [W(CO)₅(THF)] gives cyclo-(RBiS)₂[W(CO)₅]₂ (8). cyclo-(R′BiS)₂ (9) [R′ = 2,6-(Me₂NCH₂)₂C₆H₃] is formed by reaction of R′BiCl₂ and Na₂S. The structures of 1–9 were determined by single-crystal X-ray diffraction.