Electron‐Rich Organoantimony( III ) Dithiolate Complexes

Electron‐rich dithiolene complexes of the antimony( III ) PhSb moiety, formulated as [SbPh(dddt)] ( 1 ) (dddt: 5,6‐dihydro‐1,4‐ditthine‐2,3‐dithiolate) and [SbPh(EDT‐TTFS 2 )] ( 2 ) (EDT‐TTFS 2 : 4,5‐ethylenedithio‐tetrathiafulvalene‐4′,5′‐dithiolate), have been prepared by deprotection of the corresponding precursors and trapping of the intermediate dithiolates with PhSbCl 2 . Both complexes have been structurally characterized. The analysis of their single‐crystal X‐ray structures shows original supramolecular organizations governed by secondary Sb ··· S contacts, with distorted octahedral coordination geometries around the Sb center. Band‐structure calculations for complex 2 reveal only weak dispersion of the valence and conduction bands, with an energy gap of 1.68 eV. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)