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[BMIm]2[{PbMn(CO)5)}6I8] (BMIm: 1-butyl-3-methylimidazolium) is obtained by ionic liquid mediated reaction of PbI2 and Mn2(CO)10. Central is a cubelike (Pb6I8) unit containing a nonfilled Pb6 octahedron. Each Pb of this (Pb6I8) unit is terminated on its outside by Mn(CO)5, exhibiting Pb--Mn metal-to-metal bonding (280 pm). Structurally, the (Pb6I8) unit is similar to the well-known octahedral (M6Xn) cluster-type family (M = Zr, Nb, Ta, Mo, W; X = Cl, Br, I). In contrast to most similar cluster compounds, such as W6Br12 ([W6Br8]Br2/1Br4/2, according to Niggli notation) or the carbonyl cluster [Sn6{Cr(CO5)6}]2-, however, the nonfilled central Pb6 octahedron in [{PbMn(CO)5)}6I8]2- does not exhibit any metal-to-metal bonding. Structure and bonding of the title compound are validated by single-crystal structure analysis, energy-dispersive X-ray analysis (EDX), infrared spectroscopy (FT-IR), and density functional theory (DFT) calculations. Based on the isolobal principle, electronegativity considerations, bond lengths, and DFT calculations including Mulliken population analysis and natural population analysis (NPA), in sum, the charge distribution of Pb is best reflected by an oxidation state of +1. [ABSTRACT FROM AUTHOR]

The novel tin(II) oxychloride [BMIm][Sn 5 O 2 Cl 7 ] (BMIm = 1-butyl-3-methylimidazolium) is obtained by the room-temperature reaction (25 °C) of black SnO and SnCl 2 in [BMIm]Cl/SnCl 2 as an ionic liquid. The title compound can be described as composed of noncharged, infinite ∞ 1 (Sn 2 OCl 2 ) strands that are embedded in a saline matrix of [BMIm] + and [SnCl 3 ] - . The ∞ 1 (Sn 2 OCl 2 ) strands consist of a backbone of edge-sharing OSn 4/2 tetrahedra, which represent one-dimensional (1D) strands cut out of the layer-type structure of SnO. In [BMIm][Sn 5 O 2 Cl 7 ], the ∞ 1 (Sn 2 OCl 2 ) strands, which mimic a 1D semiconductor, are terminated by chlorine atoms, whereas they are interconnected by oxygen atoms in the 2D semiconductor SnO. The view of the noncharged ∞ 1 (Sn 2 OCl 2 ) strands in a saline [BMIm][SnCl 3 ] matrix is validated by dissolution experiments. Thus, electron microscopy and Raman spectroscopy show a deconstruction of [BMIm][Sn 5 O 2 Cl 7 ] single crystals after treatment with chloroform with a dissolution of [BMIm][SnCl 3 ], the formation of SnCl 2 needles, and tin oxide as a solid remain.

GaSeCl 5 O is a new inorganic molecular compound prepared from SeO 2 , SeCl 4 , and GaCl 3 at 50 °C in quantitative yield. The structure of the title compound is described by GaCl 3 (OSeCl 2 ) molecules with a tetrahedrally coordinated Ga atom and a pseudo-tetrahedrally coordinated Se atom (including lone pair of Se(IV)) that are bridged by oxygen. GaSeCl 5 O crystallizes in the polar chiral space group P 6 1 , which is rarely observed for molecular structures. The compound is characterized by X-ray structure analysis based on single crystals and powder samples, thermogravimetry, infrared and Raman spectroscopy as well as by second harmonic generation (SHG) measurements. The experimental data are complemented by density functional theory calculations. GaSeCl 5 O shows one of the strongest SHG signals known in the visible part of the electromagnetic spectrum (480-700 nm) with an SHG intensity 10 times higher than potassium dihydrogen phosphate (KDP). This is in accordance with the phase matchability and a strong dipole moment (| μ | = 8.3 D for a molecule in the crystal lattice). Such a strong SHG effect is also remarkable since GaSeCl 5 O-unlike most of the materials with strong SHG intensity-is an inorganic molecular compound.

Orange, transparent crystals of [BMIm] 2 [Mn(CO) 3 (GeI 3 ) 3 ] (BMIm: 1-butyl-3-methylimidazolium) are obtained by reacting GeI 4 , [Mn(CO) 6 ][AlCl 4 ], and Ph 3 GeH in the ionic liquid [BMIm][NTf 2 ]. [Mn(CO) 6 ][AlCl 4 ] and triphenylgermane turn out to be essential as reactive carbonyl precursors and for the reduction of GeI 4 . According to X-ray structure analysis based on single crystals, the title compound exhibits a novel {MnGe 3 } cluster unit with Mn-Ge single bonds and surprisingly short distances (236-241 pm). Although sensitive to oxygen/moisture, the carbonyl compound is stable up to a temperature of 150 °C. Mass spectrometry (MS) shows [Mn(CO) 3 (GeI 3 ) 2 ] - , [Mn(CO) 3 (GeI 3 )I] - , and [GeI 3 ] - as decomposition fragments in the gas phase. In addition to crystal structure analysis and MS, the title compound is characterized by energy-dispersive X-ray spectroscopy (EDXS), thermogravimetry (TG), optical spectroscopy (UV-visible), infrared spectroscopy (FT-IR), and density functional theory (DFT) calculations.

[BMIm]2[{PbMn(CO)5)}6I8] (BMIm: 1-butyl-3-methylimidazolium) is obtained by ionic liquid mediated reaction of PbI2 and Mn2(CO)10. Central is a cubelike (Pb6I8) unit containing a nonfilled Pb6 octahedron. Each Pb of this (Pb6I8) unit is terminated on its outside by Mn(CO)5, exhibiting Pb-Mn metal-to-metal bonding (280 pm). Structurally, the (Pb6I8) unit is similar to the well-known octahedral (M6Xn) cluster-type family (M = Zr, Nb, Ta, Mo, W; X = Cl, Br, I). In contrast to most similar cluster compounds, such as W6Br12 ([W6Br8]Br2/1Br4/2, according to Niggli notation) or the carbonyl cluster [Sn6{Cr(CO5)6}](2-), however, the nonfilled central Pb6 octahedron in [{PbMn(CO)5)}6I8](2-) does not exhibit any metal-to-metal bonding. Structure and bonding of the title compound are validated by single-crystal structure analysis, energy-dispersive X-ray analysis (EDX), infrared spectroscopy (FT-IR), and density functional theory (DFT) calculations. Based on the isolobal principle, electronegativity considerations, bond lengths, and DFT calculations including Mulliken population analysis and natural population analysis (NPA), in sum, the charge distribution of Pb is best reflected by an oxidation state of +1.