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A first example of an aryltellurium(II) compound with three different bonding modes to iodine featuring covalent and non‐covalent bonds such as two orthogonal, ambiphilic σ‐hole interactions is introduced: [MesTe(I)(I2)(I3)]−. It is a member of a series of mesityltellurenyl anions, which are formed during reactions of (MesTe)2 with ZnI2, phenanthroline (phen) and iodine. [Zn(phen)3][MesTe(I)2] (1), [Zn(phen)3][{MesTe(I)‐(I)...Te(I)Mes}{MesTeI2}] (2) and [Zn(phen)3][MesTe(I)(I2)(I3)][MesTeI2] (3) are isolated depending on the amount of iodine used. The products contain tellurium atoms bonded to a variety of iodine species (I−, μ2‐I−, I2 and I3−) and are, thus, perfectly suitable to explore the amphiphilic behavior of tellurium(II) and its relevance for the formation of non‐covalent bonds, where tellurium acts as both donor and acceptor simultaneously. The character of chalcogen and halogen bonds are evaluated by the combination of crystallographic data and computational methods. [ABSTRACT FROM AUTHOR]

In situ prepared lithium arylselenolates {LiSePh, LiSe(2,6‐Me2Ph), LiSe(2,4,6‐Me3Ph)} or ‐tellurolates {LiTePh, LiTe(2,6‐Me2Ph), LiTe(2,4,6‐Me3Ph)} react with [ReOCl3(PPh3)2] and (NBu4)Br in good yields under formation of rhenium(V) complexes of the composition (NBu4)[ReO(L)4)]. The first oxidorhenium(V) complex with four monodentate phenolato ligands, [ReO(2,6‐Me2Ph)4]−, was prepared and isolated in crystalline form. This allows a comparison of experimental and computational data of a full series of such compounds with basal O, S, Se and Te donor atoms. Similar reactions with [ReCl3(PPh3)2(CH3CN)] or [ReCl3(PMe2Ph)3] give trigonal bipyramidal rhenium(III) complexes of the compositions [Re(PPh3)(L)3(CH3CN)] or [Re(PPh3)2(L)3] depending on the chalcogenolate applied. The reported oxidorhenium(V) and rhenium(III) complexes were fully characterized by spectroscopic methods and X‐ray diffraction. The bonding situation in the rhenium(V) and rhenium(III) chalcogenolates was assessed through density functional theory calculations based on the quantum theory of atoms in molecules (QTAIM), natural bonding orbital (NBO) analysis, charge analysis, the electron localization function (ELF) maps and topological descriptors at the {3,−1} critical points such as metallicities. Expectedly, the ionicity of the rhenium‐chalcogen bonds decreases according to all three applied charge models from O to Te. Generally, the Re−Se and Re−Te bonds are more directional in the Re(III) complexes than in the oxidorhenium(V) compounds. [ABSTRACT FROM AUTHOR]

The salicylidene Schiff bases of bis(2‐aminophenyl)diselenide and ‐ditelluride react with [ReOCl3(PPh3)2] or the arylimidorhenium(V) compounds [Re(NPhR)Cl3(PPh3)2] (R = H, F, CF3) with formation of rhenium(V) complexes with tridentate {O,N,Se/Te} chalcogenolato ligands. The ligands adopt a facial coordination mode with the oxygen donors trans to the multiply bonded O2– or NPhR2– ligands. The reduction of the dichalcogenides and the formation of the chalcogenolato ligands occurs in situ by released PPh3 ligands. The absence of additional reducing agents provides good yields of products with rhenium in the high formal oxidation state "+5". A mechanism for the dichalcogenide reduction is proposed on the basis of the experimental results. In accordance with the proposed mechanism, best yields are obtained with a strict exclusion of oxygen, but in the presence of water. [ABSTRACT FROM AUTHOR]

In this paper we explore an amino functionalized selenolate unit for the synthesis of new multinuclear compounds with promising interesting properties and potential precursors of semiconductors. We present for the first time the X‐ray crystallographic structure of [Hg(SeC6H4NH2)2]2·diox (1·diox) and its copper(I) derivatives: HgCu2X2(SeC6H4NH2)2(PPh3)4·4diox [X = Br (2·4diox) and I (3·4diox)]. The compounds 1 and 2, 3 can be considered as the starting material and intermediates, respectively, for the synthesis of ternary HgII/Se/CuI nanoclusters. We also provide IR and NMR spectroscopic data and evaluate the optical features of these compounds by difuse reflectance UV/Vis spectroscopy. [ABSTRACT FROM AUTHOR]

Reactions of (NEt4)2[Re(CO)3Br3] with N-heterocyclic thiols such as 2-mercaptobenzimidazole (H2Sbenzim), 2-mercaptothiazoline (HSthiaz), or 5-mercapto-1-methyltetrazole (HSmetetraz) give rhenium(I) complexes of various compositions: (NEt4)[Re(CO)3Br2- (H2Sbenzim)], [Re(CO)3(HSthiaz)3]Br, and (NEt4)[Re2(CO)6(μ-SSmetetraz- κS)(μ-N,S-Smetetraz-κS,N)2]. Corresponding reactions with 2-mercaptopyridine (HSpy) and bis(2-pyridine)diselenide [(Sepy)2] did not give defined products in reasonable yields, whereas [Re(CO)5Br] reacts with HSpy and (Sepy)2 with formation of [Re(CO)3(HSpy)3]Br and [Re2(CO)6(Sepy)2], respectively. All reactions were performed without the addition of a supporting base and the sulfur-containing organic ligands are coordinated in their thione forms with the exception of Smetetraz- in its μS-bridging coordination mode in (NEt4)- [Re2(CO)6(μ-S-Smetetraz-κS)(μ-N,S-Smetetraz-κS,N)2], which can be regarded as thiolate. The bonding mode of the selenium containing ligands in the dimeric compound [Re2(CO)6(Sepy)2] (C-Se distance: 1.93 Å) can also best be described as selenolate. The products are stable on air at an ambient temperature. They were studied spectroscopically and by x-ray diffraction. [ABSTRACT FROM AUTHOR]