Ruthenium spectroscopic properties

Direct labeling of a biomolecule involves the introduction of a covalently linked fluorophore in the nucleic acid sequence or in the amino acid sequence of a protein or antibody. Fluorescein, rhodamine derivatives, the Alexa, and BODIPY dyes (Molecular Probes [92]) as well as the cyanine dyes (Amersham Biosciences [134]) are widely used labels. These probe families show different absorption and emission wavelengths and span the whole visible spectrum (e.g., Alexa Fluor dyes show UV excitation at 350 nm to far red excitation at 633 nm). Furthermore, for differential expression analysis, probe families with similar chemical structures but different spectroscopic properties are desirable, for example the cyanine dyes Cy3 and Cy5 (excitation at 548 and 646 nm, respectively). The design of fluorescent labels is still an active area of research, and various new dyes have been reported that differ in terms of decay times, wavelength, conjugatibility, and quantum yields before and after conjugation [135]. New ruthenium markers have been reported as well [136]. 

Grguric-Sipka S, Stepanenko IN, Lazic JM, Bartel C, Jakupec MA, Arion VB, Keppler BK (2009) Synthesis, x-ray diffraction structure, spectroscopic properties and antiproliferative activity of a novel ruthenium complex with constitutional similarity to cisplatin. Dalton Trans 3334-3339... 

We have already alluded to the diversity of oxidation states, the dominance of oxo chemistry and the cluster carbonyls. Brief mention should be made too of the tendency of osmium (shared also by ruthenium and, to some extent, rhodium and iridium) to form polymeric species, often with oxo, nitrido or carboxylato bridges. Although it does have some activity in homogeneous catalysis (e.g. of m-hydroxylation, hydroxyamination or animation of alkenes, see p. 558, and occasionally for isomerization or hydrogenation of alkenes, see p. 571), osmium complexes are perhaps too substitution-inert for homogeneous catalysis to become a major feature of the chemistry of the element. The spectroscopic properties of some of the substituted heterocyclic nitrogen-donor complexes may yet make osmium an important element for photodissociation energy research. 

Thiazyl monomer can be stabihzed by coordination to a metal, and many thionitrosyl complexes with Cr, Mo, Re, Ru, Os, Co, Rh, Ir, and Pt are known. Comparison of the spectroscopic properties and the electronic stmctures of M-NS and M NO complexes indicates that NS is a better a-donor and jr-acceptor ligand than NO. Oxygen transfer from an NO2 to an NS ligand on the same metal center occurs in ruthenium porphyrin complexes. ... 

On the other hand, the ruthenium-catalyzed addition of alkenes to alkynes involves a jr-allylruthenium intermediate [40]. Heating a 1 1 mixture of 1-octene and 1-octyne in 3 1 DMF-water at 100 °C with 5 mol% of ruthenium complex (C5H5)RuCl(cod) for 2 h gave a 1 1 adduct, the spectroscopic properties of which clearly showed it to be a branched 1,4-diene with a small amount of the regioiso-meric linear adduct (Eq. 5.26). 

K. Maruszewki, D.P. Strommen, K. Handrich, and J.R. Kincaid, Synthesis and Spectroscopic Properties of Zeolite-entrapped Bis-heteroleptic Ruthenium(II) Polypyridine Complexes. Inorg. Chem., 1991, 30, 4579 4582. 

DeWilde, W., Peelers, G., and Lunsford, J.H. 1980. Synthesis and spectroscopic properties of tris (2,2 -bipyiidine)ruthenium(II) in zeolite Y. Journal of Physical Chemistry 84, 2306-2310. 

The first ruthenium dihaloboryl Cp/Ru(CO)2BCl2 (8.102) has recently been spectroscopically characterized, although no structural data were reported [60]. As with the related iron complex CpFe(CO)2BCl2 (8.35), 8.102 exhibits the relatively downfield-shifted 11B resonance (5b 81.0) and high frequency carbonyl stretching bands (2012, 1958 cm-1), expected for a boryl system featuring poorly 7r-donating substituents. The ferrocenyl(bromo)boryl complex Cp/Ru(CO)2B(Fc)Br (8.101) has also been synthesized recently and has spectroscopic properties similar to those of the closely related iron systems 8.63 and 8.64 [92]. 

Constable, E.C. (1994) Metallosupramolecular chemistry Chem. Ind., 56-59 Constable, E.C, Cargill Thompson, A.M.W. and D.A. Tocher (1992) Into the third dimension of coordination chemistry towards starburst arrays in Supramolecular Chemistry Eds Balzani, V. and De (Zola, L. Klewer Academic Press, Dordrecht 219-233 Constable, E.C, Cargill Thompson, A.M.W. and D.A. Tocher (1992) Synthesis, characterisation and spectroscopic properties of ruthenium(II)-2,2 6, 2"-terpyridine coordination triades. X-Ray structures of 4 -(A,A-dimethylamino)-2,2 6, 2"-terpyridine and w(4 -(A,A-dimethylamino)-2,2 6, 2"-terpyridine)ruthenium(II) hex uoro-phosphate acetonitrile solvate New J. Chem., 16, 855-867 Krohnke, F (1976) The specific synthesis of pyridines and oligopyridines Synthesis, 1-24... 

Chen J, Bai F-Q, Wang J, Hao L, Xie Z-F, Pan Q-J, Zhang H-X (2012) Theoretical studies on spectroscopic properties of ruthenium sensitizers adsorbed to Ti02 film surface with connection mode for DSSC. Dyes Pigm 94(3) 459-468... 

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