The complex [[(eta 5-C5Me5)(Ph3P)Ir(mu-H)2]2Ag2(OSO2CF3)2], containing the Ag2(2+)-ion, has been synthesized; crystallographic and spectroscopic data are described.

Cyclooctadienefluorotriphenylphosphaneiridium(I) [IrF(C8H12)(PPh3)] (3) was prepared and its structure determined by single crystal X‐ray diffraction analysis. Complex 3 crystallises in the monoclinic space group P21/n. The lattice parameters are a = 931.9(3) pm, b = 1629.4(7) pm, c = 1592.9(7) pm, α = γ = 90°, β = 92.85(3)°. Number of molecules per unit cell is 4. The square planar iridium complex 3 exhibits an Ir−F bond length of 201.3(5) pm. 3 was obtained in Teflon tubes, whereas the use of glass vessels led to cyclooctadiene‐bis(triphenylphosphane)iridium(I)‐pentafluorosilicate(IV) ([Ir(C8H12)(PPh3)2][SiF5]) (4). The composition of 4 was confirmed by single crystal X‐ray diffraction analysis. 4 crystallises in the monoclinic space group P21/c. The lattice parameters are a = 1157.4(9) pm, b = 1864.4(9) pm, c = 1922.5(17) pm, α = γ = 90°, β = 96.16(7)°. The number of molecules per unit cell is 4. The square‐planar coordinated iridium cation [Ir(C8H12)(PPh3)2]+ is separated from the trigonal bipyramidal [SiF5]− anion by 461.1 pm (shortest Ir···F distance) and thus it is assumed that no interactions occur between the fluorine and iridium atoms. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Chloro(η5‐pentamethylcyclopentadienyl)(η2‐pyridine‐2‐car‐boxylato)iridium(III) [Ir(η5‐C5Me5)(η2‐C5H4N‐2‐CO2)Cl] (2) and chloro(η5‐pentamethylcyclopentadienyl)[η2‐2‐(diphenylphosphanyl)thiophenolato]iridium(III) [Ir(η5‐C5Me5)(η2‐2‐Ph2PC6H4S)Cl] (3) were prepared and their structures determined by single‐crystal X‐ray diffraction analysis. Complex 2 crystallizes in the orthorhombic space group Pbca. The number of molecules per unit cell is eight, whereas 3 crystallizes in the orthorhombic space group Pna21 and the number of molecules per unit cell is four. The coordination of the η2‐bound ligands in 2 and 3 leads to chelate bite angles N–Ir–O(2) and P–Ir–S of 77.0(2)° and 82.42(7)°, respectively. The iridium atoms in 2 and 3 are chiral and both enantiomers are present in the unit cell. The substitution of the chloro ligand in 3 affords hydrido(η5‐pentamethylcyclopentadi‐enyl)‐[η2‐2‐(diphenylphosphanyl)thiophenolato]iridium(III][Ir(η5C5Me5)(η2‐2‐Ph2PC6H4S)H] (4) and methyl(η5‐penta‐methylcyclopentadienyl)[η2‐2‐(diphenylphosphanyl)thiophen‐olato]iridium(III) [Ir(η5‐C5Me5)(η2‐2‐Ph2PC6H4S)Me] (5), respectively, in good yields. The 31P{1H} NMR resonances of 4 (δ = 33.9 ppm) and 5 (δ = 35.8 ppm) prove unambiguously that the 2‐(diphenylphosphanyl)thiophenolato ligand still remains η2‐coordinated.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

Reaction of [M(NH 3 ) 6 ]Cl 3 (M = Co, Rh, Ir) and [Ir(NH 3 ) 5 (OH 2 )]Cl 3 with (NH 4 ) 2 C 2 O 4´H2 O in aqueous solution resulted in the isolation of [M(NH 3 ) 6 ] 2 (C 2 O 4 ) 3´4 H 2 O and [Ir(NH 3 ) 5 (OH 2 )] 2 (C 2 O 4 ) 3´4 H 2 O, respectively. The complexes have been characterized by X-ray crystallography, IR and UV/VIS spectroscopy. The isomorphous compounds crystallize in the orthorhombic space group Pnnm (No. 58). Four molecules of crystal water are involved in an extended three-dimensional hydrogen bonding network. The librational modes of the lattice water around 600 cm ±1 allow the characterization of [Ir(NH 3 ) 6 ] 2 (C 2 O 4 ) 3´4 H 2 O and [Ir(NH 3 ) 5 (OH 2 )] 2 (C 2 O 4 ) 3´4 H 2 O, respectively, by IR spectroscopy. The band around 600 cm ±1 shows a significant frequency shift in the IR spectra of the hexaammine and aquapentaammine complex of iridium(III) and, by that, a distinction is possible. Wasserlo È sliche und halogenfreie Hexaamminkomplexe von Metallionen der 9. Gruppe ± Darstellung, Kristallstrukturen und Schwingungsspektren Inhaltsu È bersicht. Die halogenfreien und wasserlo È slichen Verbindungen [M(NH 3 ) 6 ] 2 (C 2 O 4 ) 3´4 H 2 O und [Ir(NH 3 ) 5 -(OH 2 )] 2 (C 2 O 4 ) 3´4 H 2 O (M = Co, Rh, Ir) konnten durch Umsetzung von [M(NH 3 ) 6 ]Cl 3 und [Ir(NH 3 ) 5 (OH 2 )]Cl 3 mit (NH 4 ) 2 C 2 O 4´H2 O in wa È ssriger Lo È sung dargestellt werden. Die Komplexe wurden durch Einkristallstrukturanalyse, IR und UV/VIS Spektroskopie charakterisiert. Die isomorphen Verbindungen kristallisieren orthorhombisch in der Raumgruppe Pnnm (No. 58). Die vier Kristallwassermoleku È le sind an einem dreidimensionalen Netzwerk von Wasserstoffbru È kkenbindungen beteiligt. Die Librationen dieser Kristallwassermoleku È le liegen etwa bei 600 cm ±1 und ermo È glichen die Charakterisierung von [Ir(NH 3 ) 6 ] 2 (C 2 O 4 ) 3´4 H 2 O und [Ir(NH 3 ) 5 (OH 2 )] 2 (C 2 O 4 ) 3´4 H 2 O durch IR Spektroskopie. Diese Bande bei etwa 600 cm ±1 zeigt eine deutliche Verschiebung in den IR Spektren des Hexaamminiridium(III) und des Aquapentaamminiridium(III) Komplexes und ermo È glicht somit deren Unterscheidung.

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