Permethylated Disila[2]metallocenophanes of Group 14 and 15 Elements

Abstract

Abstract Permethylated disila[2]metallocenophanes of silicon, germanium, tin, lead, 2 a – d , (tetrelocenophanes) and antimony, 3 a , b , (pnictogenocenophanes) are described. In the case of antimony, a chloro‐substituted stibonocenophane, 3 a , as well as cationic stibonocenophanium tetrachloroaluminate and tetraphenylborate salts, 3 b [X] (X=[AlCl 4 ], [BPh 4 ]), were synthesized. These represent the first examples of metallocenophanes of any Group 15 element. All compounds were studied in solution and in the solid state. Without exception the ansa ‐bridge exerts a strong influence on the bending angle of the two Cp‐ligands. For disila[2]plumbocenophane, 2 d , its reactivity towards Group 15 halides was probed. Treatment of disila[2]plumbocenophane, 2 d , with two equivalents of phosphorus(III) chloride or arsenic(III) chloride, results in a ring‐opening reaction and gives the bis(dihalopnictogenyl)‐substituted products, 4 a , b .