Iodidomesityltellurium(II) iodidotrimesitylditellurium(II)(Te—Te)

In the title compound, C₉H₁₁ITe·C₂₇H₃₃ITe₂ or (Mes)TeI·(Mes₂Te)TeI(Mes) (Mes is mesityl or 2,4,6‐trimethylphenyl), a strong Te...I interaction of 3.3157 (9) Å links the Te atom of an iodidomesityltellurium(II) moiety, (Mes)TeI, and an I atom of the iodidotrimesitylditellurium(II) unit, (Mes₂Te)TeI(Mes). Further weak Te...I contacts of 4.0818 (9) Å give rise to one‐dimensional chains along the b axis in the crystal structure. An intramolecular C—H...π(arene) interaction is present in the (TeMes₂)TeI(Mes) moiety, with a C...Cg distance of 3.497 (9) Å and a C—H...Cg angle of 142° (where Cg is the centroid of a mesityl ring of the Mes₂Te moiety).     

Density functional theory study of Te(CN)2, Te(CN)(NC), and Te(NC)2 and their isomerizations

The equilibrium structures of Te(CN)₂, Te(CN)(NC), and Te(NC)₂ and three isomerization reactions: Te(CN)₂ ? Te(CN)(NC), Te(CN)(NC) ? Te(NC)₂, and Te(CN)₂ ? Te(NC)₂ were studied in the gas-phase using density functional theory. Three functionals (B3LYP, BLYP, and BHLYP) were employed to characterize the low-lying electronic singlet and triplet TeC₂N₂ isomers. The basis sets for carbon and nitrogen used were of double-ζ plus polarization quality with additional s- and p-type diffuse functions, DZP++. For the tellurium atom, the LANL2DZ (ECP) basis set was used. The energetic ordering (kcal mol^?1) (B3LYP) including zero-point vibrational energy corrections for the singlet ground state isomers follows: Te(CN)₂ (0.0, global minimum) < Te(CN)(NC) (15.4) < Te(NC)₂ (29.8). Electrostatic potentials and average local ionization energies of the ground state Te(CN)₂, Te(CN)(NC), and Te(NC)₂ isomers provide some guidance as to sites for noncovalent and covalent interactions. Energetics such as the different forms of electron affinities, ionization energies, and singlet–triplet gaps were also reported. Further the theoretical rate constants for the isomerization reactions were evaluated using transition state theory. We predict that these isomers may crystallize in similar patterns, if stable, as does Se(CN)₂.     

[(Mes3Sn)2MoO4], ein monomeres Triorganozinnmolybdat

[(Mes₃Sn)₂MoO₄], a Monomeric Triorganotin Molybdate Mes₃SnBr (Mes = 1, 3, 5‐trimethylphenyl) reacts with (NBu₄)₂[Mo₆O₁₉] in the presence of (NBu₄)OH (in CH₃CN as solvent) to form [(Mes₃Sn)₂MoO₄]. Alternatively the title compound can be obtained from the reaction of [MoO₂(acac)₂] (acac = 2, 4‐pentadionate) with Mes₃SnOH in isopropanol. [(Mes₃Sn)₂MoO₄] forms monoclinic crystals, space group C2/c, with a = 2271.6(3) pm, b = 825.2(1) pm, c = 2739.9(5) pm, β = 90.96(2)°. The crystal structure consists of isolated molecules in which a tetrahedral MoO₄ unit is connected to two terminal Mes₃Sn groups. The Mo‐O distances range from 169.6(4) to 181.1(3) pm and the Sn‐O distance is 204.8(3) pm.     

Synthese und Kristallstrukturen von (PPh4)2[TeS3] · 2 CH3CN und (PPh4)2[Te(S5)2]

Synthesis and Crystal Structures of (PPh₄)₂[TeS₃] · 2 CH₃CN and (PPh₄)₂[Te(S₅)₂] (PPh₄)₂[TeS₃] · 2 CH₃CN was obtained by the reaction of PPh₄Cl, Na₂S₄ and Te in acetonitrile. With sulfur it reacts yielding (PPh₄)₂[Te(S₅)₂]. The crystal structures of both products were determined by X-ray diffraction. (PPh₄)₂[TeS₃] · 2 CH₃CN: triclinic, space group P1 , Z = 2, R = 0.041 for 4 629 reflexions; it contains trigonal-pyramidal [TeS₃]^2? ions with an average Te? S bond length of 233 pm. (PPh₃)₂[Te(S₅)₂]: monoclinic, P2₁/n, Z = 2, R = 0.037 for 2 341 reflexions. In the [Te(S₅)₂]^2? ion the tellurium atom has a nearly square coordination by four S atoms. Along with the Te atoms each of the two S₅ groups forms a ring with chair conformation.     

Magnesium Cyanide or Isocyanide?

Preference for the binding mode of the CN^? ligand to Mg (Mg?CN vs. Mg?NC) is investigated. A monomeric Mg complex with a terminal CN ligand was prepared using the dipyrromethene ligand ^MesDPM which successfully blocks dimerization. While reaction of (^MesDPM)MgN(SiMe₃)₂ with Me₃SiCN gave the coordination complex (^MesDPM)MgN(SiMe₃)₂?NCSiMe₃, reaction with (^MesDPM)Mg(nBu) led to (^MesDPM)MgNC?(THF)₂. A Mg?NC/Mg?CN ratio of ≈95:5 was established by crystal‐structure determination and DFT calculations. IR studies show absorbances for CN stretching at 2085 cm^?1 (Mg?NC) and 2162 cm^?1 (Mg?CN) as confirmed by ¹³C labeling. In solution and in the solid state, the CN ligand rotates within the pocket. The calculated isomerization barrier is only 12.0 kcal mol^?1 and the ¹³C NMR signal for CN decoalesces at ?85 °C (Mg?NC: 175.9 ppm, Mg?CN: 144.3 ppm). Experiment and theory both indicate that Mg complexes with the CN^? ligand should not be named cyanides but are more properly defined as isocyanides.     

β‐Diketiminate‐Stabilized Magnesium(I) Dimers and Magnesium(II) Hydride Complexes: Synthesis,Characterization, Adduct Formation,and Reactivity Studies

The preparation and characterization of a series of magnesium(II) iodide complexes incorporating β‐diketiminate ligands of varying steric bulk and denticity, namely, [(ArNCMe)₂CH]^? (Ar=phenyl, (^PhNacnac), mesityl (^MesNacnac), or 2,6‐diisopropylphenyl (Dipp, ^DippNacnac)), [(DippNCtBu)₂CH]^? (^tBuNacnac), and [(DippNCMe)(Me₂NCH₂CH₂NCMe)CH]^? (^DmedaNacnac) are reported. The complexes [(^PhNacnac)MgI(OEt₂)], [(^MesNacnac)MgI(OEt₂)], [(^DmedaNacnac)MgI(OEt₂)], [(^MesNacnac)MgI(thf)], [(^DippNacnac)MgI(thf)], [(^tBuNacnac)MgI], and [(^tBuNacnac)MgI(DMAP)] (DMAP=4‐dimethylaminopyridine) were shown to be monomeric by X‐ray crystallography. In addition, the related β‐diketiminato beryllium and calcium iodide complexes, [(^MesNacnac)BeI] and [{(^DippNacnac)CaI(OEt₂)}₂] were prepared and crystallographically characterized. The reductions of all metal(II) iodide complexes by using various reagents were attempted. In two cases these reactions led to the magnesium(I) dimers, [(^MesNacnac)MgMg(^MesNacnac)] and [(^tBuNacnac)MgMg(^tBuNacnac)]. The reduction of a 1:1 mixture of [(^DippNacnac)MgI(OEt₂)] and [(^MesNacnac)MgI(OEt₂)] with potassium gave a low yield of the crystallographically characterized complex [(^DippNacnac)Mg(μ‐H)(μ‐I)Mg(^MesNacnac)]. All attempts to form beryllium(I) or calcium(I) dimers by reductions of [(^MesNacnac)BeI], [{(^DippNacnac)CaI(OEt₂)}₂], or [{(^tBuNacnac)CaI(thf)}₂] have so far been unsuccessful. The further reactivity of the magnesium(I) complexes [(^MesNacnac)MgMg(^MesNacnac)] and [(^tBuNacnac)MgMg(^tBuNacnac)] towards a variety of Lewis bases and unsaturated organic substrates was explored. These studies led to the complexes [(^MesNacnac)Mg(L)Mg(L)(^MesNacnac)] (L=THF or DMAP), [(^MesNacnac)Mg(μ‐AdN₆Ad)Mg(^MesNacnac)] (Ad=1‐adamantyl), [(^tBuNacnac)Mg(μ‐AdN₆Ad)Mg(^tBuNacnac)], and [(^MesNacnac)Mg(μ‐tBu₂N₂C₂O₂)Mg(^MesNacnac)] and revealed that, in general, the reactivity of the magnesium(I) dimers is inversely proportional to their steric bulk. The preparation and characterization of [(^tBuNacnac)Mg(μ‐H)₂Mg(^tBuNacnac)] has shown the compound to have different structural and physical properties to [(^tBuNacnac)MgMg(^tBuNacnac)]. Treatment of the former with DMAP has given [(^tBuNacnac)Mg(H)(DMAP)], the X‐ray crystal structure of which disclosed it to be the first structurally authenticated terminal magnesium hydride complex. Although attempts to prepare [(^MesNacnac)Mg(μ‐H)₂Mg(^MesNacnac)] were not successful, a neutron diffraction study of the corresponding magnesium(I) complex, [(^MesNacnac)MgMg(^MesNacnac)] confirmed that the compound is devoid of hydride ligands.     

Addition of Isocyanides to Tetramesityldigermene: A Comparison of the Reactivity between Surface and Molecular Digermenes

The reaction of benzyl isocyanide, tert‐butyl isocyanide, and 2,6‐dimethylphenyl isocyanide with tetramesityldigermene (Mes₂Ge=GeMes₂) was examined. Whereas the addition of benzyl isocyanide gave the C?NC activation product, Mes₂Ge(CH₂Ph)Ge(CN)Mes₂, tert‐butyl isocyanide, and 2,6‐dimethylphenyl isocyanide did not give stable adducts, rather the rate of conversion of the digermene to the corresponding cyclotrigermane was accelerated. A comparison between the reactivity of the isocyanides with Mes₂Ge=GeMes₂ and the Ge(100)‐2×1 surface was made and some insights into the surface chemistry are offered.     

Synthesis and structure of silyl acetonitriles

An efficient route for the preparation of Mes₂HSiCH₂CN (1) and (Mes₂HSi)₂CHCN (2) is reported (Mes = 2,4,6-trimethylphenyl). Although the X-ray analyses for 1 and 2 reveal the CH_nCN functionality (n = 1, 2) to be shielded by the Mes₂HSi group, hydrolysis under basic conditions gave exclusively Mes₂HSiOH (3), as a result of hydroxide-induced Si-C bond cleavage. In the solid state 3 is a tetramer forming an eight membered ring by H-bond interactions.     

Probing the aromaticity of bis(diazolo)pyrazine radical anions

The aromaticity of a series of heterocyclic radical anions of bis(diazolo)pyrazine type, X(CN)₂N₂(CN)₂Y (X, Y = O, S, Se, Te) was explored by the methods of electron density of delocalized bonds (EDDB) and gauge-included magnetically induced currents (GIMIC). The existence of T-aromaticity that encloses the entire molecule, which was due to delocalization of seven β-electrons, was shown. The degree of aromaticity depends on the nature of the X(Y) heteroatom and varies in the series S > O > Se > Te.     

A Diazabutadiene stabilized Nickel(0) Cyclooctadiene Complex: Synthesis,Characterization and the Reaction with Diphenylacetylene

The reaction of [Ni(COD)₂] with one equivalent of DAB^Mes (DAB^Mes = (2,4,6‐Me₃C₆H₂)N=C(Me)‐C(Me)=N(2,4,6‐Me₃C₆H₂)) affords a mixture of the compound [Ni(DAB^Mes)₂] ( 2 ) and starting material [Ni(COD)₂]. The crystallographically characterized, diamagnetic complex 2 can be obtained in a stoichiometric reaction of [Ni(COD)₂] and two equivalents of DAB^Mes. This reaction can be accelerated by addition of 1‐chloro‐fluorobenzene or methyl iodide. In the presence of 1‐chloro‐fluorobenzene, [Ni(DAB^Mes)(COD)] ( 3 ) is available via reaction of [Ni(COD)₂] and one equivalent of DAB^Mes. The crystallographically characterized complex 3 reacts with diphenylacetylene to afford [Ni(DAB^Mes)(Ph‐C≡C‐Ph)] ( 4 ). A long‐wavelength absorption band in the UV‐Vis spectrum of this compound has to be assigned to a mixed MLCT/LL′CT transition, as quantum chemical calculations reveal.     

Reaktionen von Diorganogallium(indium)fluoriden. Die Kristallstruktur von Mes2InF

Reaction of Diorganogallium(indium) Fluorides. The Crystal Structure of Mes₂InF Mes₂GaF ( 1 ) reacts with t-BuNH₂ at 20°C to the amine adduct [Mes₂Ga(F)(t-BuNH₂)] ( 2 ). Treatment of 1 with H₂S gives after a redox reaction γ-S₈-Sulfur (Muthmanns' Sulfur) ( 3 ) as the only isolated product. When i-Pr₂InF ( 4 ) is reacted with [SnCl₂(dioxane)] in toluene at 70°C one yields after workup [i-PrInCl₂(dioxane)] ( 5 ), which is formed after ligand exchange and reaction with dioxane. 2 and 5 were investigated by NMR-, IR- and MS-techniques. In addition, 2 · 2,5 THF, 3, 5 and Mes₂InF were characterized by an X-ray structure determination. According to that 2 · 2,5 THF contains dimeres, associated by hydrogen brigdes, while 5 possesses a polymeric structure with bridging dioxane molecules. 3 forms eightmembered rings with C ₂-symmetry. Me₂InF is a trimer in the solid state with an In₃F₃-backbone.     

Tetraaryldiborane(4) Can Emit Dual Fluorescence Responding to the Structural Change around the B–B Bond

We report the successful synthesis of tetramesityldiborane(4) (Mes₄B₂) through the reductive coupling of a dimesitylborinium ion. Owing to the steric protection conferred by the mesityl groups, Mes₄B₂ shows exceptional chemical stability and remains intact in water. Single-crystal X-ray analysis revealed that Mes₄B₂ has an orthogonal geometry, where the B–B center is completely hidden by the mesityl groups. Remarkably, Mes₄B₂ emits dual fluorescence at 460 and 620 nm, both in solution and in the solid state. Theoretical calculations showed that Mes₄B₂ in the excited S₁ state adopts a twisted or planar geometry, which is responsible for the shorter- or longer-wavelength fluorescence, respectively. The intensity ratio of the dual fluorescence is sensitive to the viscosity of the medium, which suggests that Mes₄B₂ has potential as a ratiometric viscosity sensor.     

On the reaction of aminobis(diorganylamino)phosphanes with halogenophosphanes—P-hydrogeno(iminophosphoranyl)-halogenophosphanes and P-hydrogeno(iminophosphoranyl)-σ2, λ3-iminophosphanes

Reactions of triaminophosphane (R₂N)₂P–NH₂, (R = ¹Pr) 1a, with aminodihalogenophosphanes ¹Pr₂N–PX₂, 2a–c [X = CL (a), Br (b), I(c)], in the presence of a base yielded the P-hydrogeno-iminophosphoranyl-halogenophosphanes (R₂N)₂PH = N–PX–N(¹Pr)₂ 4a–c [X = Cl (a), Br (b), I(c)]. Analogous reactions between 1a and 1b (b: R = c-hexyl) and chloroiminophosphane (Cl–P = N–Mes^*, (Mes^* = 2,4,6-^tBu₃C₆H₂) 6 , gave the P-hydrogeno(iminophosphoranyl)-σ²,λ³-iminophosphanes, (R₂N)₂PH = N–P = N–Mes^* 8a and 8b. In solution 8a, 8b eliminated amine, yielding σ², λ³-iminophosphanyl-substituted 1,3,2,4-diazadiphosphetidines [(R₂N)PN(P = N–Mes^*)]₂, 10a, 10b , and 11 ( 10a and 10b : cis; 11: trans). The X-ray structure analyses of compounds 4a, 4b, 8a, and 11 are discussed. © 1996 John Wiley & Sons, Inc.     

Synthesen und Eigenschaften von Tetrakis(perfluoralkyl)tellur Te(Rf)4 (Rf = CF3, C2F5, C2F5, C3F7, C4F9)

Synthesis and Properties of Tetrakis(Perfluoroalkyl)Tellurium Te(R_f)₄ (R_f = CF₃, C₂F₅, C₃F₇, C₄F₉) Te(CF₃)₄ is obtained from the reaction of Te(CF₃)Cl₂ with Cd(CF₃)₂ complexes as a complex with e. g. CH₃CN, DMF. It is a light and temperature sensitive hydrolysable liquid. The reaction with fluorides yields the complex anion [Te(CF₃)₄F]⁻, with fluoride ion acceptors the complex cation [Te(CF₃)₃]⁺. With traces of water an acidic solution is formed. Te(CF₃)₄ acts as a trifluoromethylation reagent. The reaction with XeF₂ gives hints for the formation of Ye(CF₃)₄F₂. Properties and NMR spectra are discussed. The much more stable complexes of Te(R_f)₄ (R_f = C₂F₅, C₃F₇, C₄F₉) are formed from the reaction of TeCl₄ with the corresponding Cd(R_f)₂ complexes.     

F2P(NEt2)3 – Difluorphosphorane als vielseitige Fluoridierungsmittel

F₂P(NEt₂)₃ – Difluorophosphanes as Versatile Fluoridation Agent F₂P(NEt₂)₃ ( 1 ), prepared by the reaction of P(NEt₂)₃ with SF₄ (3:2) in Et₂O at –78°C, acts as fluoridation agent on Lewis acids such as AlMe₃, GaMe₃, or [Mes₃V(THF)] by transfer of a F ^– ion. The products [FP(NEt₂)₃][Me₃MF] [M = Al ( 2 ), Ga ( 3 )] and [FP(NEt₂)₃][Mes₃VF] ( 4 ) were characterized by NMR, IR and MS techniques. With 1 and 4 an X‐ray structure determination could be performed. According to them 1 consists of trigonal‐bipyramidal λ⁵‐phosphane molecules with an occupation of the axial positions by F^– ligands. In 4 the centers of the cations [FP(NEt₂)₃]⁺ and of the anions [Mes₃VF]^– are distorted terahedrally coordinated.     

Synthese und Kristallstrukturen von (NEt4)2[TeS3], (NEt4)2[Te(S5)(S7)] und (NEt4)4[Te(S5)2][Te(S7)2]

Synthesis and Crystal Structures of (NEt₄)₂[TeS₃], (NEt₄)₂[Te(S₅)(S₇)], and (NEt₄)₄[Te(S₅)₂][Te(S₇)₂] (NEt₄)₂[TeS₃] was obtained by the reaction of NEt₄Cl, Na₂S₄ and tellurium in acetonitrile. It reacts with sulfur, yielding (NEt₄)₂[Te(S₅)(S₇)], which is transformed to (NEt₄)₄[Te(S₅)₂][Te(S₇)₂] by recrystallization from hot acetonitrile. According to the X-ray structure analysis, crystals of (NEt₄)₂[TeS₃] are monoclinic (space group P2₁/c) and form twins with the twinning plane (001); they contain pyramidal TeS₃^2– ions. (NEt₄)₂[Te(S₅)(S₇)] forms triclinic twins (space group P1) with the twinning plane (010). In the [Te(S₅)(S₇)]^2– ion an S₅ and an S₇ atom group are bonded in a chelate manner to the tellurium atom, which has square coordination. (NEt₄)₄[Te(S₅)₂][Te(S₇)₂] (monoclinic, space group P2₁/c) contains two kinds of anions, the known [Te(S₅)₂]^2– and the new [Te(S₇)₂]^2– ion which has two S₇ chelating groups.     

Zur Chemie des Dimesityleisens. X. Mesityleisenkomplexe [FeMes(X)]2 mit zentraler {Fe2(μ-Mes)2}-Einheit (Mes = C6H2-2,4,6-(CH3)3)

Chemistry of Dimesityl Iron. X. Mesityl Iron Complexes [FeMes(X)]₂ with a Central {Fe₂(μ-Mes)₂} Unit (Mes = C₆H₂-2,4,6-(CH₃)₃) Dimeric complexes [{MesFe(OAryl)}₂] with coordination number (CN) of 3 are obtained from Fe₂Mes₄ 1 by partial acidolyses with 2,6-di-tert-butyl-substituted phenols (HOAryl). 1 reacts with 1,3-diketones in a molar ratio of 1:2 to [{MesFe(diketonate)}₂] with CN 4. A central {Fe₂(μ-Mes)₂}-unit with short Fe—Fe distances of 2.56 to 2.63 Å ( 1: 2.615 Å) is found in both types of complexes. The mixed ligand complexes react with an excess of phenol or diketone to {Fe(OAryl)₂} or {Fe(diketonate)₂}, respectively. 1 reacts with HOAryl in the molar ratio of 1:1 to [Fe₂(μ-Mes)₂Mes(OAryl)]. The structures of [Fe₂(μ-Mes)₂(OC₆H₂-2,6-tBu₂-4-CH₃)₂] ( 3 ), [Fe₂(μ-Mes)₂Mes(OC₆H₂-2,4,6-tBu₃)] ( 5 ) and [Fe₂(μ-Mes)₂{(tBuCO)₂CH}₂] ( 9 ) are presented.     

Synthesis, characterization and structural studies of dithiocarbamate derivatives of 2,2,6,6-tetramethyl-1-oxa-4,4-diiodo-4-tellura-2,6-disilacyclohexane,O[Si(CH3)2CH2]2TeI(dtc)

Five new hetero-organotellurium (IV) dithiocarbamates O[Si(CH₃)₂CH₂]₂TeIS₂CN(CH₂CH₂)₂ (1), O[Si(CH₃)₂CH₂]₂TeIS₂CN(CH₂CH)₂ (2), O[Si(CH₃)₂CH₂]₂TeIS₂CN(CH₂CH₂)₂O (3), O[Si(CH₃)₂CH₂]₂-TeIS₂CN(CH₂CH₂)₂S (4) and O[Si(CH₃)₂CH₂]₂TeIS₂CN(CH₂CH₂)₂CH₂ (5) were prepared from the 2,2,6,6-tetramethyl-1-oxa-4,4-diiodo-4-tellura-2,6-disilacyclohexane and the corresponding dithiocarbamate (dtc) sodium salts in ethanol. The compounds were characterized by means of Elemental Analyses, FAB MS, IR, ¹H, ¹³C, ¹²⁵Te NMR spectroscopy. The crystal structures of 1, 3 and 4 were determined. Dithiocarbamate ligands display an anisobidentate chelating coordination mode on interacting with the tellurium center in all compounds. The Te(IV) immediate environment can be described as that of a sawhorse structure in which the lone pair is apparently stereochemically active and occupying an equatorial position in a distorted trigonal bipyramid. The two methylene groups occupy the other equatorial positions with a sulfur atom of the dithiocarbamate group and the iodine atom occupying the axial positions. The solid state structures of 3 and 4 exhibit important intermolecular interaction Te?S(2B). This interaction results in the formation of a dimer, which is better described as a distorted octahedron with an apparently inactive lone pair.     

Perfluoralkyltellur-Verbindungen: Oxidation von (CF3)2Te Darstellungen und Eigenschaften von (CF3)2TeCl2, (CF3)2TeBr2, (CF3)2Te(ONO2)2 und (CF3)2TeO [1]

Perfluorosalkyl Tellurium Compounds: Oxidation of (CF₃)₂Te; Preparations and Properties of (CF₃)₂TeCl₂, (CF₃)₂TeBr₂, (CF₃)₂Te(ONO₂)₂, and (CF₃)₂TeO From the oxidation of (CF₃)₂Te with Cl₂, Br₂, O₂, and ClONO₂ the new trifluoromethyl tellurium compounds (CF₃)₂TeCl₂, (CF₃)₂TeBr₂, (CF₃)₂TeO, and (CF₃)₂Te(ONO₂)₂ are prepared. The ¹⁹F, ¹³C and ¹²⁵Te n.m.r. spectra, the vibrational and mass spectra as well as the chemical properties of these compounds are described. By variation of the reaction conditions CF₃TeCl₃ and CF₃TeBr₃ are also formed. It has not been possible to isolate (CF₃)₂TeI₂, but there is some evidence that it is formed as an intermediate. (CF₃)₂Te reacts with ozone to a very unstable compound, which decomposes at low temperature.     

Diiodobis(diphenyltelluride)mercury(II), [(Ph2Te)2HgI2]

Diiodobis(diphenyltelluride)mercury(II), [(Ph₂Te)₂HgI₂], is formed during the reaction of [(PhTe)₂Hg] with HgI₂ in refluxing THF. The same product can be obtained from a pressure reaction between PhTeI₃ and elemental mercury. The mercury atom is co‐ordinated in a distorted tetrahedral environment with I‐Hg‐I angles of 117?. Long range I···Te contacts of about 3.8 Å link the [(Ph₂Te)₂HgI₂] units to infinite chains along the b axis of the unit cell.