Rhenium synthesis

Hydrido complexes of rhenium synthesis and reactivity, D. Giusto, Inorg. Chim. Acta, Rev., 1972, 6,91-101(61). 

Another synthesis of pyrogaHol is hydrolysis of cyclohexane-l,2,3-trione-l,3-dioxime derived from cyclohexanone and sodium nitrite (16). The dehydrogenation of cyclohexane-1,2,3-triol over platinum-group metal catalysts has been reported (17) (see Platinum-GROUP metals). Other catalysts, such as nickel, rhenium, and silver, have also been claimed for this reaction (18). 

Although these methods were applied for the synthesis of a number of various phthalocyanines with different central atoms (e.g., H2, Cu, Zn, Ni, Pt, Pd, Lu, etc.) not all metal phthalocyanines can be prepared by one of these methods. For example, the synthesis of silicon phthalocyanine, rhenium phthalocyanine and boron subphthalocyanine need more drastic conditions. In the following, an overview of the synthesis of phthalocyanines containing all central metals which have hitherto been inserted into the ring is given. 

Although the number of applications of olefin metathesis to transition metal complexes is small compared to the number of applications in organic synthesis, this field is becoming increasingly important. Spectacular examples are the double RCM reactions of copper phenanthroline complexes as a synthetic route to catenanes [113] or a recently reported approach to steric shielding of rhenium complex terminated sp-carbon chains [114]. 

Scheme 21 Synthesis of rhenium complexes by the reaction of the rhenium chlorides with polysulfide dianions...

Scheme 26 Synthesis of rhenium and niobium polysulfido complexes from the corresponding doubly bonded complexes...

Scheme 31 Synthesis of ruthenium and rhenium disulfido complexes by the use of (TMS)2S as a sulfur reagent...

Hubberstey P, Suksangpanya U (2004) Hydrogen-Bonded Supramolecular Chain and Sheet Formation by Coordinated Guranidine Derivatives 111 33-83 Hupp JT (2006) Rhenium-Linked Multiporphyrin Assemblies Synthesis and Properties 121 145-165... 

Saladino R, Crestini C, Costanzo G, DiMauro E (2005) On the Prebiotic Synthesis of Nucle-obases, Nucleotides, Oligonucleotides, Pre-RNA and Pre-DNA Molecules. 259 29-68 Santos I, Paulo A, Correia JDG (2005) Rhenium and Technetium Complexes Anchored by Phosphines and Scorpionates for Radiopharmaceutical Applications. 252 45-84 Santos M, see Szathmdry E (2005) 259 167-211... 

To transfer the original synthesis to technetium was not very convenient, as it would have to start from TcBr(CO)5 (32a). A preparation has recently been reported which starts from 3a or 19a in refluxing THF and used BH3 as the reducing agent [36]. The complex 31a could be isolated in 60-70% yield, based on Tc, and has been characterized by i.r. specroseopic methods as well as Tc and Cl analysis, and compared to its rhenium congener (Scheme 5). 

Scheme 17. Synthesis of mixed oxo-alkyi complexes of high valency technetium and rhenium...

H. Y. Chung, M. B. Weinberger, J. B. Levine, A. Kavner, J. M. Yang, S. H. Tolbert, and R. B. Kaner, Synthesis of Ultra-incompressible Superhard Rhenium Diboride at Ambient Pressure, Jour. Amer. Chem. Soc., 316,436 (2007). 

Aspects of the apparatus for the synthesis using metal atoms are described. The reactions of the atoms of rhenium, tungsten, and osmium with hydrocarbons including alkanes are described. It is shown that metal atom reactions with alkanes can give isolable organometallic compounds including l-alkylidene compounds. 

M. Gottschaldt, D. Koth, D. Muller, I. Klette, S. Rau, H. Gorls, B. Schafer, R. P. Baum, and S. Yano, Synthesis and structure of novel sugar-substituted bipyridine complexes of rhenium and 99m-technetium, Chem. Eur. 13 (2007) 10273-10280. 

Vada, S., Hoff, A., Adnane, E., Schanke, D., and Holmen, A. 1995. Fischer-Tropsch synthesis on supported cobalt catalysts promoted by platinum and rhenium. Topics Catal. 2 155-62. 

Das, T.K., Jacobs, G., Patterson, P.M., Conner, W.A., Li, J., and Davis, B.H. 2003. Fischer-Tropsch synthesis Characterization and catalytic properties of rhenium promoted cobalt alumina catalysts. Fuel 82 805-15. 

Scheme 2. Synthesis of bifunctional chelators and conjugates based on the rhenium(l)-cyclopentadienyl core.

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