SYNTHESIS AND REACTIONS OF STERICALLY HINDERED alpha-NAPHTHYL-AND CYCLOHEXYLANTIMONY(V) DERIVATIVES

摘要

Interhaolgen and halo-pseudohalogens IX (X = Cl, Br, N_3, NCO), (SCN)_2, S and TeCl_4 add oxidatively to (alpha-C_10H_7)_3 Sb to afford (alpha-C_10H_7)_3Sb(SCN)_2, (alpha-C_10H_7)_3 SbS and (alpha-C_10H_7)_3SbCl_2, respectively. Reactions of R_3SbCl_2 (R - alpha-C_10H_7, cycle-C_6H_11) with MY (M = Ag, K, Na; Y = SCN, CN, NCO, N_3) yielded the penta-coordinate products, R_3Sb(SCN)_2, R_3Sb(NCO)_2, (alpha-C_10H_7)_3Sb(CN)_2 and (alpha-C_10H_7)_3Sb(N_3)_2. The compounds (alpha-C_10H_7)_3SbI(SCN) and (alpha-C_10H_7)_3SbI(SeCN) are also accessible by selective replacement reactions of (alpha-C_10H_7)3SbICl or (alpha-C_10H_7)_3SbIBr with the corresponding metal salts. Hydrolysis of R_3SbCl_2(R = alpha-C_10H_7, cycle-C_6H_11) afforded (R_3SbCl)_2O-type compounds. (alpha-C_10H_7)_3Sb inserts into the N-chloro bond of N-chlorosuccinimide and N-cholorophalimide to give (alpha-C_10H_7)_3Sb(Cl)NCO(CH_2)_2CO and (alpha-C_10H_7)_3Sb(Cl)NCO(C_6H_4)CO. These haloimides may also be prepared by the interaction of (alpha-C_10H_7)_3SbCl_2 with the corresponding sodium salt of the imido moiety.