Syntheses and structures of [8,8′-µ-(OSO 2 O)(1,2-C 2 B 9 H 10 ) 2 -3-Co] -and [(8-Ph-1,2-C 2 B 9 H 10 )-3-Co-(1′,2′-C 2 B 9 H 11 ] -ions and of [(8-dioxane-1,2-C 2 B 9 H 10 )-3-Co-(1′,2′-C 2 B 9 H 11 )] zwitterion are described. All compounds result on dimethyl sulfate induced nucleophilic B-substitution of the parent cobalta-carborane sandwich ion under acid catalysis. A general mechanism is proposed. Constitutions of all compounds are inferred from the mass and multinuclear NMR spectroscopy and all structures are established by X-ray diffraction. Selected NMR and X-ray data are presented.

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Treatment of RuCl2(η2-Ph2PCH2CH2OCH3)2 with various chelating diamines permitted the isolation of the corresponding RuCl2(η1-Ph2PCH2CH2OCH3)2(diamine) complexes in high yield (diamine = 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-phenylenediamine, 1,8-diaminonaphthalene, 2,2‘-bipyridine, 1,10-phenanthroline). In solution, all complexes prefer the trans-chloro cis-phosphine arrangement, as deduced by NMR spectroscopy. X-ray studies showed that in the solid state all three possible isomers of the octahedral RuCl2P2(diamine) complexes are present. The reaction of the RuCl2(η1-Ph2PCH2CH2OCH3)2(diamine) complexes with 1 equiv of AgSbF6, AgBF4, or TlPF6 leads to the abstraction of one chloride by simultaneously coordinating one ether oxygen to ruthenium and forming monocationic [RuCl(η1-Ph2PCH2CH2OCH3)(η2-Ph2PCH2CH2OCH3)(diamine)]+ compounds. If a large excess of silver or thallium salt is used, the dichloro complexes are converted to the [Ru(η2-Ph2PCH2CH2OCH3)2(diamine)]2+ dications. In the case of 1,2-phenylendiamine as coligand, the corresponding dication is only observed in traces. NMR spectroscopic investigations and X-ray structural analyses confirm the η1 and η2 coordination of the ether−phosphine ligands in the corresponding mono- and dicationic ruthenium(II) complexes.

A comprehensive 31P solid-state NMR study of Ru(eta1-Ph2PCH2CH2OCH3)2(eta2-en)Cl2 (en = ethylenediamine) (1), by 1D (contact time variation, inversion-recovery, SPARTAN) and 2D techniques (homonuclear J-resolved, SECSY) indicated that the crystal structure of 1 should be complex. The single-crystal x-ray structure determination confirmed the presence of eight independent molecules in the asymmetric unit, with 31P isotropic chemical shifts in the range 27.3-40.1 ppm, while the spans of the phosphorus chemical shift tensors are of the order of 170 ppm. Based on unique structural features and NMR data, one molecule has been tentatively assigned.