Heterometallic ruthenium

Dias, E.L., Grubbs, R.H., Synthesis and investigation of homo- and heterometallic ruthenium olefin metathesis catalysts exhibiting increased activities, Organometallics 1998, 17 2758-2767. 

Porphyrazines have also been used to prepare metal-metal bonded dimers with ruthenium and osmium, specifically homometallic dimers comprised of two metallic octaethylporphyrazine and heterometallic dimers comprised of one metallic oc-taethylporhyrazine ligand and one metallic octaethylporphyrin ligand have been reported (189-191). The major bonding interactions that occur in these systems are directly between the two metal centers. 

No nitrido complexes of ruthenium(VIII) have been isolated. For osmium, the only well-established osmium(VIII) nitrido species is [0s(0)3(N)] , which has been well documented in CCC (1987). A number of heterometallic complexes formed by the interaction of [0s(0)3(N)] with a second metal center have been reported. In these complexes, the [0s(0)3(N)] ion acts as a... 

Rearrangements of clusters, i.e. changes of cluster shape and increase and decrease of the number of cluster metal atoms, have already been mentioned with pyrolysis reactions and heterometallic cluster synthesis in chapter 2.4. Furthermore, cluster rearrangements can occur under conditions which are similar to those used to form simple clusters, e.g. simple redox reactions interconvert four to fifteen atom rhodium clusters (12,14, 280). Hard-base-induced disproportionation reactions lead to many atom clusters of rhenium (17), ruthenium and osmium (233), iron (108), rhodium (22, 88, 277), and iridium (28). And the interaction of metal carbonyl anions and clusters produces bigger clusters of iron (102, 367), ruthenium, and osmium (249). 

Heterometal alkoxide precursors, for ceramics, 12, 60-61 Heterometal chalcogenides, synthesis, 12, 62 Heterometal cubanes, as metal-organic precursor, 12, 39 Heterometallic alkenes, with platinum, 8, 639 Heterometallic alkynes, with platinum, models, 8, 650 Heterometallic clusters as heterogeneous catalyst precursors, 12, 767 in homogeneous catalysis, 12, 761 with Ni—M and Ni-C cr-bonded complexes, 8, 115 Heterometallic complexes with arene chromium carbonyls, 5, 259 bridged chromium isonitriles, 5, 274 with cyclopentadienyl hydride niobium moieties, 5, 72 with ruthenium—osmium, overview, 6, 1045—1116 with tungsten carbonyls, 5, 702 Heterometallic dimers, palladium complexes, 8, 210 Heterometallic iron-containing compounds cluster compounds, 6, 331 dinuclear compounds, 6, 319 overview, 6, 319-352... 

Collman, J. R, Harford, S. T., Maldivi, R, Marchon, J.-C. (1998b). Unusual molecular orbital ordering in molybdenum-ruthenium heterometallic porphyrin dimers Structural and magnetic evidence, J. Am. Chem. Soc., 120 7999. 

Furthermore, a rigid helical macrocycle 114 was prepared in 56% yield through the self-assembly of (S,S) or R,R)-105 and dimetallic complex 113 under similar conditions (Scheme 5.26) [51]. Circular dichroism (CD) spectra of these three molecules indicated their enantiomeric properties. The heterometallic platinum(II)-ruthenium(II) macrocycle 114 was selected for photophysical study. It exhibited an interesting luminescence behavior. Emission... 

The heterometallic derivative Fe2(GO)6(Se)2 /x-HGG(GGMe) Os3(GO)io and its ruthenium homolog Fe2(GO)6(Se)2 /x-HGG(GGMe) Ru3(GO)io both contain an alkyne bound in parallel fashion to the trinuclear cluster and also show Se-G bonds. ... 

The chemistry of metallabenzenes has been extensively investigated. However, their synthesis by the insertion method is poorly understood and difficult to predict. Salzer et al. recently reported an excellent method to generate bis(metallabenzene) ruthenium complexes (Equation (3)). With this strategy, heterometallic compounds can also be obtained. However, these reactions are sometimes more complicated than one would anticipate. For example, the reactions of the pentadienyl sandwich complex 21 with [Fe2(CO)9] afforded the heterometallic complex 22 in 80% yield, which clearly involved a relatively complicated process to allow the transfer of the pentadienyl group from Ru to the Fe center. 

The addition of OMe to cluster-coordinated GO has been used in the electrospray spectrometry of metal carbonyl complexes.Heterometallic clusters such as Gp Fe(GO)(/x-GO)2Ru2(GO)4(//-H) /x-MeG(GOO)Gl have been obtained upon carbonyl substitution with MeG(Gl)HGOOH on the tetra-heterometallic precursor. An efficient synthetic method for Ru3(GO)i2 starting from ruthenium dioxide hydrate has been reported in the presence of formic or acetic acid, carboxylate complexes are obtained. These favor the reductive carbonylation of nitrobenzene to aniline and A,iV -diphenylurea. 

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