1,2-Dichalcogenolylium Ions (C3Cl3E3)+ from Equilibria Involving Dichalcogen Dichlorides E2Cl2 (E = S, Se, Te) − Syntheses and Crystal Structures of (C3Cl3S2)Cl, (C3Cl3Se2)Cl, and (C3Cl3Te2)2[Te2Cl10]

Abstract

The reaction of tetrachlorocyclopropene with SeCl4 or TeCl4 in CH2Cl2 under solvothermal conditions at 120 °C and 90 °C, respectively, is a suitable route to 1,2‐dichalcogenolylium ions. Yellow crystals of (C3Cl3Se2)+Cl− or red crystals of {(C3Cl3Te2)+}2[Te2Cl10]2− are formed in such reactions. The reaction of hexachloropropene with elemental sulfur — the well‐known route to 3,4,5‐trichloro‐1,2‐dithiolylium chloride (C3Cl3S2)Cl — turned out not to be transferable to selenium and tellurium chemistry. NMR investigations of the reaction solutions allowed to set up reaction equilibria also involving hexachloropropene and dichalcogen dichlorides E2Cl2. The crystal structures of all three compounds were determined by X‐ray diffraction. All contain planar, five‐membered ring shaped cations (C3Cl3E2)+ (E = S, Se, Te). Short E−E bonds (S−S 201, Se−Se 231, Te−Te 266 pm) indicate substantial π‐bonding and charge delocalisation. The anion in (C3Cl3Te2)2[Te2Cl10] consists of two tetragonal pyramidal [TeCl5]− units linked by long Te−Cl bridges to centrosymmetric dimers in the form of edge‐sharing double octahedra. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

Halide anions driven self-assembly of haloperfluoroarenes: Formation of one-dimensional non-covalent copolymers

“…This is the case, among others, in monohalopyridinium halides and monohaloanilinium halides where the monodentate cation forces the potentially polydentate anion to form a single XB and gives rise to discrete adducts [17]. When in the same systems the cation bears two or three halogen atoms, its ability to function as a di-or tridentate XB donor frequently can elicits the di-or tridentate potential of halide anions and infinite chains [18] or (6,3) nets [19] can be formed, respectively.…”

“…Two different thermal events can be detected (by visual inspection and by DSC analyses) at 327 K (minor) and 468 K (major); 1 H NMR (250 MHz, CD 3 CN): d 5.1 (br, NH), 3.8 (6H, brq, NH-CH 2 ), 3.6 (6H, brt, N-CH 2 ); 19 (2-(2,3,5,6-tetrafluoro-4-bromophenyl)aminoethyl)ammonium iodide (5) Tris- (2-(2,3,5,6-tetrafluoro-4-bromophenyl)-aminoethyl)amine was prepared in 65% isolated yield from tris(2-aminoethyl)amine and pentafluorobromobenzene through a procedure strictly similar to that described above for the iodo analogue. 1 H NMR (250 MHz, CDCl 3 ): d 4.3 (3H, br, NH), 3.5 (6H, t, J = 6 Hz, NH-CH 2 ), 2.8 (6H, t, J = 6 Hz, N-CH 2 ), 19 3396, 2841, 1641, 1493, 1260, 1155, 1076, 956, 827 cm À1 . 1.0 mL of 57% aqueous HI solution is mixed with 2.0 mL of MeOH and anhydrous Na 2 SO 4 is added in sufficient amount to remove water. The solution is filtered and added to a solution of tris- (2-(2,3,5,6-tetrafluoro-4-bromophenyl (6) In the first reaction step tris(2-hydroxyethoxyethyl)amine was synthesized.…”

“…1 H NMR (250 MHz, CDCl 3 ): d 4.35 (t, 6H, J = 4.5 Hz), 3.76 (t, 6H, J = 4.5 Hz), 3.56 (t, 6H, J = 5.8 Hz), 2.74 (t, 6H, J = 5.8 Hz). 19 1630,1477,1357,1271,1092,970,865, 797 cm À1 . 1.0 mL of 57% aqueous HI solution is mixed with 2.0 mL of MeOH and anhydrous Na 2 SO 4 is added in sufficient amount to remove water.…”

Oxidative Addition of Ph2TeCl2to a Dimethylplatinum(II) Complex: Effects of Secondary Bonding in the Platinum−Tellurium Products

“…The bond length Pt−Te = 2.5730(5) Å, with Te trans to Cl, is shorter than that in the only other platinum(IV)−tellurium-bonded complex [PtMe 2 (Ph 2 SnTe) 2 (bu 2 bpy)], in which Te is trans to methyl and has Pt−Te = 2.719(1) Å . Most known complexes with platinum−tellurium bonds contain square planar platinum(II) in combination with R 2 Te or RTe - ligands, and the Pt−Te distances range from 2.51 to 2.76 Å, determined mostly by the nature of the trans ligand. ,,− The shortest is found in [PtCl 2 (MeSCH 2 CH 2 TeAr)] 12 [Pt−Te trans to chloride = 2.514(1) Å], and the longest, in trans -[Pt(4-PhC 6 H 4 Te)(SiMe 3 )(PEt 3 ) 2 ] 6 [Pt−Te trans to silyl = 2.764(2) Å].

1 View of the molecular structure of 2 .

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7 Oxygen, sulfur, selenium and tellurium

“…The 1,2-dichalcogenolylium ions, (C 3 Cl 3 Se 2 ) ϩ Cl Ϫ and {(C 3 Cl 3 Te 2 ) ϩ } 2 -[Te 2 Cl 10 ] 2 , have been prepared from the reaction of tetrachlorocyclopropene and SeCl 4 or TeCl 4 , respectively, whilst (C 3 Cl 3 S 2 ) ϩ Cl Ϫ was obtained from the reaction of elemental sulfur with hexachloropropene. 76 The X-ray crystal structures of the three salts show that the cations are planar, five-membered ring structures whilst the sulfur and selenium analogues feature close contacts between the chalcogen and chloride atoms. The reactions of several phosphine selenides with dihalogens and sulfuryl chloride have been studied.…”