Complexes of Stiboranium Mono-, Di-, and Trications.

Reaction of Ph2 SbCl3 with 2,2'-bipyridine and Me3 SiOSO2 CF3 releases chlorobenzene, which is interpreted as a reductive (SbV /SbIII ) elimination from a complex of a stiboranium cation. Conversely, reactions of Ph2 SbCl3 with 4-methylpyridine-N-oxide and AgOSO2 CF3 give redox-resistant complexes with the generic formulae [Ph2 SbCl3-x Lx+1 ][OTf]x , including a compound containing a pnictogen(V) trication.

Substitution Reactions at Dipp BIAN Supported Fluoroantimony Cations Yielding Cyanoantimony and Azidoantimony Cations.

This work presents new cationic coordination complexes of antimony with the 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (Dipp BIAN) ligand system. The fluoroantimony complexes [SbF(Dipp BIAN)][OTf]2 and [SbF2 (Dipp BIAN)][OTf] have been successfully isolated and characterized. The fluorine substituent in the Lewis acidic complex [SbF(Dipp BIAN)][OTf]2 can be selectively replaced without degradation of the Sb-Dipp BIAN interaction to give the first dicationic azido and cyano derivatives, [Sb(CN)(Dipp BIAN)][OTf]2 and [Sb(N3 )(Dipp BIAN)][OTf]2 , which have been isolated and structurally characterized.