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The novel tellurium rhenium carbonyls [TeI2Re(CO)5][AlCl4] (1), [BMIm][Te2I4(μ-I)2Re(CO)4] (2), {Te3I2(μ-I)3(μ3-I)}Re(CO)3 (3) and [BMIm][(Te2)3{Re(CO)3}2{Re(CO)4}3] (4) were prepared by reacting TeI4 and Re2(CO)10 in ionic liquids (ILs). [TeI2Re(CO)5][AlCl4] (1) was obtained in a mixture of [BMIm]Cl (BMIm: 1-butyl-3-methylimidazolium) and AlCl3 (ratio: 1 : 1) and contains a [TeI2Re(CO)5]+ cation. Increasing the amount of AlCl3 ([BMIm]Cl : AlCl3 = 1 : 2) results in [BMIm][Te2I4(μ-I)2Re(CO)4] (2) with the anion [Te2I4(μ-I)2Re(CO)4]−. At a [BMIm]Cl to AlCl3 ratio of 1 : 3, {Te3I2(μ-I)3(μ3-I)}Re(CO)3 (3) was realized with a Te3I3 ring and μ3-coordinating iodine. Finally, [BMIm][(Te2)3{Re(CO)3}2{Re(CO)4}3] (4) was prepared in [BMIm][OTf] (OTf: triflate) and contains the ufosan-like anion [(Te2)3{Re(CO)3}2{Re(CO)4}3]− with three Te22− and two Re(CO)3+ units that establish a distorted heterocuban-like cage. The compounds were characterized by single-crystal structure analysis, energy dispersive X-ray (EDX) analysis, thermogravimetry (TG), and infrared spectroscopy (FT-IR). The course of the reaction and the formation of the four novel tellurium-rhenium carbonyls can be directly correlated to the reaction conditions and especially to the acidity of the IL. [ABSTRACT FROM AUTHOR]

Dark red and brick red transparent crystals of FeI4{GeI3Fe(CO)3}2 ( 1) and (GeI3)2Fe(CO)4 ( 2) were obtained by reacting GeI4 and Fe2(CO)9 or Fe3(CO)12 in a mixture of [BMIM]Cl and AlCl3 as ionic liquid (BMIm = 1-butyl-3-methylimidazolium). According to X-ray structure analysis based on single crystals, the title compounds exhibit cluster units with Fe-Ge bonds. FeI4{GeI3Fe(CO)3}2 consists of two GeI2I1/2-Fe(CO)3I2/2 units that are interlinked by a distorted octahedral FeI6/2 group. (GeI3)2Fe(CO)4 consists of two GeI3 units that are connected by a square planar Fe(CO)4 group with a linear Ge-Fe-Ge unit. Depending on the synthesis conditions, interestingly, (GeI3)2Fe(CO)4 crystallizes either in P21/ n ( 2a) or in P 1 ( 2b). 2a exhibits a more dense packing, whereas 2b exhibits shorter intermolecular I-I distances. Both title compounds are temperature labile and highly sensitive to oxygen, moisture and illumination, including X-ray irradiation. They decompose with release of CO in absence of certain CO atmosphere. In addition to crystal structure analysis the compounds were characterized by energy dispersive X-ray (EDX) analysis, thermogravimetry (TG) and infrared spectroscopy (FT-IR). [ABSTRACT FROM AUTHOR]

The phosphorus interhalides [PBr4][IBr2] (1) and [PBr4]2[I5Br7] (2) were prepared by reaction of PBr5 and the interhalogen IBr in the ionic liquid [MeBu3N][N(Tf)2] (N(Tf)2: bis(trifluoromethylsulfonyl)amide). [PBr4][IBr2] (1) consists of tetrahedral [PBr4]+ cations and linear [IBr2]− anions. [PBr4]2[I5Br7] (2) also contains [PBr4]+ cations as well as the iodine bromide anion [I5Br7]2−. The latter represents the yet largest known polyiodinebromide. Moreover, (2) shows remarkable halogen release (IBr and Br2) of 96.8 wt% below 300 °C. For the ternary system P–Br–I, (1) and (2) are the first compounds that were characterized by crystal structure analysis. Composition, bonding situation and properties were further validated by energy dispersive X-ray (EDX) analysis, thermogravimetry (TG) and Raman spectroscopy. [ABSTRACT FROM AUTHOR]

The bimetallic metal–organic framework Cu–Ru-BTC with the stoichiometric formula Cu2.75Ru0.25(BTC)2·xH2O, which is isoreticular to HKUST-1, was successfully prepared in a direct synthesis using mild reaction conditions. The partial substitution of Cu2+ by Ru3+ centers in the paddlewheel structure and the absence of other Ru-containing phases was proven using X-ray absorption spectroscopy. [ABSTRACT FROM AUTHOR]

The phosphorus interhalides [PBr4][IBr2] (1) and [PBr4]2[I5Br7] (2) were prepared by reaction of PBr5 and the interhalogen IBr in the ionic liquid [MeBu3N][N(Tf)2] (N(Tf)2: bis(trifluoromethylsulfonyl)amide). [PBr4][IBr2] (1) consists of tetrahedral [PBr4]+ cations and linear [IBr2]− anions. [PBr4]2[I5Br7] (2) also contains [PBr4]+ cations as well as the iodine bromide anion [I5Br7]2−. The latter represents the yet largest known polyiodinebromide. Moreover, (2) shows remarkable halogen release (IBr and Br2) of 96.8 wt% below 300 °C. For the ternary system P–Br–I, (1) and (2) are the first compounds that were characterized by crystal structure analysis. Composition, bonding situation and properties were further validated by energy dispersive X-ray (EDX) analysis, thermogravimetry (TG) and Raman spectroscopy. [ABSTRACT FROM AUTHOR]