On the chemistry of fluoroorgano derivatives of Group 13 elements: Part 3. Syntheses of pentafluorophenylindium dibromide, In(C6F5)Br2·2D (D=THF, C5H5N), and related compounds—single crystal structure analyses of In(C6F5)Br2·2THF and In(acac)Br2·2THF

In(C6F5)Br2·2D (D=THF, pyridine) are selectively and almost quantitatively formed through oxidative addition of C6F5Br to InBr in THF solution or dichloromethane–pyridine mixtures. The constitution of In(C6F5)Br2·2THF is confirmed by a single crystal structure analysis (monoclinic, P21/c, Z=4, a=1694.3(2), b=1421.5(2), c=813.42(9) pm, β=100.3(1)°, Rall=0.1072). Reactions of In(C6F5)Br2·2THF and Mg(C6F5)Br in diethylether after addition of 4-dimethylaminopyridine (DMAP) yield In(C6F5)3·DMAP. In[SC(S)N(C2H5)2]3 is formed by treatment of In(C6F5)Br2·2THF with NaSC(S)N(C2H5)2 while acidic hydrolysis with aqueous HBr quantitatively gives InBr3·nH2O and C6F5H. Reactions of In(C6F5)Br2·2THF with an aqueous solution of pentane-2,4-dione (acetylacetone, Hacac) in THF quantitatively yield In(acac)Br2·2THF and C6F5H. The constitution of this compound is established by a single crystal structure analysis (orthorhombic, Pbcn, Z=4, a=1314.9(2), b=928.5(1), c=1468.4(2) pm, Rall=0.0347).