Electron‐Rich Organoantimony(III) Dithiolate Complexes

Abstract

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‐TTFS2)] (2) (EDT‐TTFS2: 4,5‐ethylenedithio‐tetrathiafulvalene‐4′,5′‐dithiolate), have been prepared by deprotection of the corresponding precursors and trapping of the intermediate dithiolates with PhSbCl2. 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)

Preparation and characterization of catena-[bromo(tetrahydrofuran-O)(2-thioxo-1,3-dithiole-4,5- dithiolato)antimony(III)], [Br(THF)Sb(dmit)]n

“…The intramolecular Sb-S bond lengths and chelate angles in these Sb III -dmio compounds are similar to the values found for the Sb III -dmit compounds. Fourmigué and coworkers have recently [26] extended their study of neutral phenylantimony(III) complexes of electron rich dithiolates to such complexes as 12 and 13, in Fig. 2.…”

Radical CpNi(dithiolene) and CpNi(diselenolene) complexes: Synthetic routes and molecular properties

“…For example, titanium, tin, antimony and zinc dithiolene complexes such as [Cp 2 Ti(dithiolene)] [37], [Bu 2 Sn(dithiolene)] [38], [PhSb(dithiolene)] [39] or (NR 4 ) 2 [Zn(dithiolene) 2 ] [40] have been reported for that purpose. In these complexes, the dithiolene ligand is present as 1,2-dithiolate(2−) form.…”

“…These reactions should be performed in a non-polar solvent (CH 2 Cl 2 , benzene and toluene) because both reactants are neutral. The neutral [Ni(dithiolene) 2 ] complexes with soluble substituents (Ph, Me) on the dithiolene ligand react with 1 at room temperature to afford [CpNi(dphedt)], [CpNi(phedt)] and [CpNi(dmedt)] in moderate yields (50-62%, entries[38][39][40][41][42][43]. On the other hand, the use of Pd and Pt complexes of dphedt resulted in lower yields (entries[44][45][46] than with the corresponding Ni complexes.…”

Covalently bonded compounds of heavy group 15/16 elements – Synthesis, structure and potential application in material sciences

“…Known solid state structures of compounds of the general type RM(ER') 2 (type II) with threecoordinated group 15 atoms (M) in the formal oxidation state +III and two-coordinated chalcogen (E) atoms are almost exclusively limited to the corresponding antimony sulfides [66,67,68,69,70,71,72,73,74,75] and bismuth sulfides. [76] In contrast, only two compounds, In both molecules, the three-coordinated bismuth atoms adopt a corner of a trigonal pyramid as is exemplarily shown for (Me 3 Si) 2 CHBi{TeSi(SiMe 3 ) 3 } 2 (Fig.…”