Linear, mixed-valent homocatenated tri-tin complexes featuring Sn-Sn bonds

Abstract

A series of tri-tin complexes((LSn)-Sn-Ph)(3)Xwith triple-decker structures (L-Ph= 2,5-di(o-pyridyl)-3,4-diphenylpyrrolate; X = Cl, AlCl4, OTf, and PF6) was synthesized by reducingL(Ph)SnClwith (LiBBu3H)-Bu-s and subsequent reactions. Structural characterization of((LSn)-Sn-Ph)(3)Clrevealed a Sn-Sn-Sn core, and DFT calculations suggest that its HOMO is primarily sigma-bonding along the tri-tin framework.((LSn)-Sn-Ph)(3)Clreacts with W(CO)(5)THF to afford((LSn)-Sn-Ph)(2)(W(CO)(5))(2)andL(Ph)SnCl, implying that((LSn)-Sn-Ph)(3)Clmay exhibit dynamic behavior in solution.