Synthese,Charakterisierung und Struktur von Carbonylund Hydrido-Isocyanatokomplexen des Rutheniums

Synthesis, Characterization, and Structure of Carbonyl and Hydrido Isocyanato Complexes of Ruthenium [Ru(CO)H(NCO)(PPh₂Me)₃] is formed during the reaction between [RuCl₃(PPh₂Me)₃] and NaOCN in EtOH. The compound crystallizes in the monoclinic space group P2₁/n (a = 1256.4(4), b = 1487.2(2), c = 1993.5(5) pm, β = 97.28(1)°, Z = 4). The distorted octahedral coordination sphere of Ru^II contains the phosphine ligands in meridional arrangement, their P atoms forming a plane together with the hydride ligand. The reaction of [RuCl₃(PPh₃)₂] with NaOCN in EtOH yields [Ru(NCO)(CO)(CH₃COO)(PPh₃)₂] with trans coordinated Ph₃P ligands. The formation of hydrido, carbonyl and acetato ligands are due to the reaction of the transition metal with the solvent ethanol.     

Synthesis and Crystal Structures of [TeI3][GaI4] and [TeI3][InI4]

The compounds [TeI₃][MI₄] (M = Ga, In) were obtained as air sensitive black crystals by the reactions of Te, I₂ and Ga or In in vacuum sealed ampoules. The gallium compound crystallizes in the structural type of [SCl₃][AlCl₄]: monoclinic system, space group Pc (No. 7), a = 7.211(11), b = 7.2340(9), c = 15.67(2) Å and β = 102.51(6)°. The indium derivative crystallizes in the orthorhombic space group Pna2₁ (No. 33), a = 14.752(2), b = 7.1915(6) and c = 23.391(5) Å, with two crystallographically independent formula units per asymmetric unit. The structures consist of tetrahedral GaI₄^– or InI₄^– and trigonal pyramidal TeI₃⁺ units. Additionally, in both structures the tellurium atoms establish three weak interactions with iodine atoms of the MI₄^– units to form a distorted octahedral Te_{3 + 3} coordination sphere.     

Synthese und Kristallstruktur von [Fe(MeCN)6][Fe2OCl6]

Synthesis and Crystal Structure of [Fe(MeCN)₆][Fe₂OCl₆] [Fe(MeCN)₆][Fe₂OCl₆] ( 2 ) is obtained by passing dry air through a solution of FeCl₂ in acetonitrile in almost quantitative yield. 2 crystallises in the trigonal space group R 3 [a = b = 12.121(1), c = 29.875(6) Å, Z = 6]. The oxygen atom in the Fe₂OCl₆ anion occupies the 3 position and causes therefore an Fe–O–Fe angle of 180°. The refinement in the triclinic space group P1 leads to a slightly bent arrangement of the Fe–O–Fe fragment.     

Rhenium Complexes with p-Fluorophenylisocyanide

p-Fluorophenylisocyanide (CNPh^pF) reacts with [Re(CO)₅Br] under stepwise exchange of the carbonyl ligands depending on the conditions applied. The reaction stops with the formation of fac-[Re(CO)₃Br(CNPh^pF)₂] in boiling THF. An ongoing carbonyl exchange is observed at higher temperatures, e. g. in refluxing toluene, with the final formation of the [Re(CNPh^pF)₆]⁺ cation. The progress of the reactions has been studied by ¹⁹F NMR spectroscopy and the structures of [Re(CO)Br(CNPh^pF)₄] and [Re(CNPh^pF)₆](BPh₄) have been elucidated by X-ray diffraction.     

A Complete Triad of Zero-Valent 17-Electron Monoradicals of Group 7 Elements Stabilized by m-Terphenyl Isocyanides

The first consistent series of mononuclear 17-electron complexes of three Group 7 elements has been isolated in crystalline form and studied by X-ray diffraction and spectroscopic methods. The paramagnetic compounds have a composition of [M⁰(CO)(CNp-F-Ar^DArF2)₄] (M=Mn, Tc, Re; Ar^DArF2=2,6-(3,5-(CF₃)₂C₆H₃)₂C₆H₂F) and are stabilized by four sterically encumbering isocyanides, which prevent the metalloradicals from dimerization. They have a square pyramidal structure with the carbonyl ligands as apexes. The frozen-solution EPR spectra of the rhenium and technetium compounds are clearly anisotropic with large ⁹⁹Tc and ^185,187Re hyperfine interactions for one component. High-field EPR (Q band and W band) has been applied for the elucidation of the EPR parameters of the manganese(0) complex.