Syntheses,Crystal Structures,and Properties of New Ternary Chalcogenides of Group 4 Metals: Rb4Ti3S14, Cs4Zr3S14, K4Hf3Se14, and K4ZrHf2Se14

The new ternary compounds Rb₄Ti₃S₁₄, Cs₄Zr₃S₁₄, K₄Hf₃Se₁₄, and K₄ZrHf₂Se₁₄ were prepared by reacting the respective transition metals in alkali metal polychalcogenide melts. Two crystallographically independent transition metal cations are present that are coordinated by eight chalcogen atoms (Q) in an irregular fashion or by seven chalcogen atoms yielding a distorted pentagonal bipyramid. The M(1)Q₈ and M(2)Q₇ polyhedra are connected by sharing common edges or trigonal faces leading to the formation of infinite linear one‐dimensional anionic chains running parallel to the [101] direction. The chains are separated by alkali metal cations. The optical band gaps determined are 1.59 eV for Rb₄Ti₃S₁₄, 2.35 eV for Cs₄Zr₃S₁₄, and 2.02 eV for K₄Hf₃Se₁₄. In‐situ X‐ray powder diffractometry demonstrates that Rb₄Ti₃S₁₄ decomposes at 430 °C into Rb₂S₅ and TiS. During the cooling cycle the re‐formation of the polysulfide is observed. According to this result the polysulfide could be prepared using TiS instead of metallic Ti as well.     

Herstellung von 1,2,4‐Trithiolan‐, 1,2,4,5‐Tetrathian‐ sowie 1,2,3,5,6‐Pentathiepan‐S‐oxiden und deren Reaktionen mit (Ph3P)2Pt(η2‐C2H4). Kristallstrukturanalyse von 3,3,5,5‐Tetraphenyl‐1,2,4‐trithiolan‐1‐oxid

Metal Complexes of Functionalized Sulfur‐containing Ligands. XVII Synthesis of S ‐Oxides of 1,2,4‐Trithiolane, 1,2,4,5‐Tetrathiane as well as 1,2,3,5,6‐Pentathiepane, and their Reactions with (Ph₃P)₂Pt(η²‐C₂H₄). X‐Ray Structure Analysis of 3,3,5,5‐Tetraphenyl‐1,2,4‐trithiolane 1‐oxide 3,3,5,5‐Tetraphenyl‐1,2,4‐trithiolan ( 1 ) was oxidized using m‐chloroperbenzoic acid to give, selectively, the 3,3,5,5‐tetraphenyl‐1,2,4‐trithiolane 1‐oxide ( 2 ). 2 was characterized structurally. The reaction of octamethyl tetrathiadispiro[3.2.3.2]dodecane‐2,9‐dione ( 3 ) with trifluoroperacetic acid at –50 °C yielded the corresponding 5‐oxide 4 . Oxidation of octamethyl pentathiadispiro[3.3.3.2]tridecane‐2,9‐dione ( 5 ) with m‐chloroperbenzoic acid at 0 °C gave the 12‐oxide 6 . Treatment of 2 with two equivalents of (Ph₃P)₂Pt(η²‐C₂H₄) ( 7 ) afforded a mixture (1 : 1) of the complexes (Ph₃P)₂PtSCPh₂S ( 8 ) and (Ph₃P)₂Pt(η²‐Ph₂C=S=O) ( 9 ), respectively.     

Extraction of Ternary Alloys: Synthesis and Crystal Structure of [K([2.2.2]crypt)]Cs7[Sn9]2(en)3

The compound [K([2.2.2]crypt)]Cs₇[Sn₉]₂(en)₃ ( 1 ) was synthesized from an alloy of formal composition KCs₂Sn₉ by dissolving in ethylenediamine (en) followed by the addition of [2.2.2]crypt and toluene. 1 crystallizes in the orthorhombic space group Pcca with a = 45.38(2), b = 9.092(4), c = 18.459(8) Å, and Z = 4. The structure consists of Cs₇[Sn₉]₂ layers which contain [Sn₉]^4– anions and Cs⁺ cations. The layers are separated by [K([2.2.2]crypt)]⁺ units. In the intermetallic slab (Cs₇[Sn₉]₂)^– compares the arrangement of pairs of symmetry‐related [Sn₉]^4– anions with the dimer ([Ge₉]–[Ge₉])^6– in [K([2.2.2]crypt)]₂Cs₄([Ge₉]–[Ge₉]), in which the clusters are linked by a cluster‐exo bond. The shortest distance between atoms of such two clusters in 1 is 4.762 Å, e. g. there are no exo Sn‐Sn bonds. The [Sn₉]^4– anion has almost perfect C_4v‐symmetry.     

Development of palladium-carbene catalysts for telomerization and dimerization of 1,3-dienes: from basic research to industrial applications

The following account summarises recent developments in the area of palladium-catalysed telomerisation and dimerisation reactions of 1,3-dienes. The most active types of catalyst, palladium-carbene complexes, were tested in pilot plant and proved to be industrially viable.