Synthesis of cis‐ and trans‐[Fe(CN)2(CNtBu)4] in a One‐Pot Procedure from Fe2(CO)9 and tert. ButylisocyanideThe reaction of Fe2(CO)9 with tert. butyl isocyanide in the presence of 10 bar of carbon monoxide leads to the formation of the mononuclear trigonal bipyramidal compound [Fe(CO)3(CNtBu)2] with two axially coordinated isocyanide ligands. If the same reaction is carried out without additional carbon monoxide being present in the solution, a 1:1 mixture of the isomeric octahedral complexes cis‐ and trans‐[Fe(CN)2(CNtBu)4] is produced via a complex redox reaction involving the reductive cleavage of isocyanide ligands. The molecular structures of the product compounds is going to be discusssed. The crystal structures of cis‐ and trans‐[Fe(CN)2(CNtBu)4] are mainly determined by the ability of the cyano ligands to act as hydrogen bond acceptor sites.

The reaction of the octahedral complexes cis‐ or trans‐[Ru(C≡N‐tBu)4(CN)2], (Ru(CN)2), with the photochemically active [bis(bipyridyl)bibenzimidazole‐ruthenium(II)], (RubiH2), component via hydrogen bond association results in the formation of supramolecular aggregates with modified photophysical properties. The first structural characterization of a supramolecular adduct is reported, in which the N–H functions of the ruthenium bound bibenzimidazole ligand via hydrogen bonds serve as an interface directly toward a cyanide ligand acting as a bridge to another transition metal. In addition, the maximum stoichiometry of the supramolecular associates is estimated by NMR titration experiments and association constants of the hydrogen bonded adducts are determined by the decay of the emission intensity during the titration experiments.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Cyanide Bridged Coordination Polymers from cis‐ or trans‐[Ru(tBuNC)4(CN)2] and MnCl2: About the Influence of Different Topologies on the Magnetic Properties of MaterialsThe reaction of cis‐ or trans‐[Ru(tBuNC)4(CN)2] with MnCl2 as an additional transition metal fragment yields the one dimensional coordination polymers {cis‐[Ru(CN)2(tBuNC)4] MnCl2}n, (1), and {trans‐[Ru(CN)2(tBuNC)4]MnCl2}n, (2), with a different arrangement of the metal centers caused by the different stereochemistry of the starting compounds. The variation of the Ru‐C‐N‐Mn geometry nevertheless leads to significant differences in the magnetic properties of 1 and 2. The coordination polymer derived from trans‐[Ru(tBuNC)4(CN)2] shows a more efficient antiferromagnetic intrachain interaction between the manganese centers compared to the cis‐derivative.

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The title compound, [Cu(C5H9N)4]Cl·H2O, was obtained from the reaction of copper(II) chloride hydrate with KCN in the presence of two equivalents of tert‐butyl­isocyanide. The reaction proceeds via the reduction of copper and the formation of (CN)2. The compound shows a tetra­hedrally surrounded CuI centre, with the CuI ion and the water O atom being situated on crystallographic twofold axes. The crystal structure contains infinite chains of alternating solvent mol­ecules and Cl− anions, with additional weak C—H⋯Cl or C—H⋯O inter­actions with the [Cu(CNtBu)4] cations.

The title compound, [Rh2Ru(CN)2Cl2(C8H12)2(C5H9N)4], was obtained from the reaction of the chloro­(1,5‐cyclo­octa­diene)rhodium(I) dimer with trans‐dicyano­tetra­(tert‐butyl isocyanide)ruthenium(II) by cleavage of the chloro bridges in the dimeric rhodium starting complex. The mol­ecular structure shows the Ru atom in a nearly ideal octa­hedral coordination geometry, whereas the Rh atoms are situated in square‐planar ligand environments. The central ruthenium ion is located on a crystallographic twofold axis. The crystal structure is realized by infinite chains of the trinuclear complex units which are connected by C—H⋯Cl inter­actions. These chains are further linked by another C—H⋯Cl inter­action to produce the observed three‐dimensional structure.

The title compound, [Ni(C5H9N)3(CO)], was prepared from Ni(CO)4 and a tenfold excess of tert-butyl isocyanide. It crystallizes with two symmetry-independent mol­ecules per asymmetric unit. The central Ni atom of each independent mol­ecule has a nearly perfect tetra­hedral coordination environment, comprising one carbon monoxide and three isocyanide ligands. The title compound is the first structurally characterized Ni0 compound with a mixed CO/RNC coordination.