Organoruthenium complexes

Reaction of organoruthenium complexes with C-H bonds was first demonstrated for Ru(dmpe)2(Np)(H) ... 

Within the last few years a number of papers appeared in an area of increasing importance for organic chemistry Organoruthenium complexes are now frequently used to form carbon-carbon bonds in a number of ways. Reagents used in this field include cyclopentadienyl complexes like [CpRu(COD)Cl] or [CpRu(PPh)2Cl] as well as tetravalent cyclo-pentadienylruthenium derivatives and oAers. 

Nolan, S. P. Solution Thermochemistry of Ligand Substitution Reactions Involving Organoruthenium Complexes, Comments Inorg. Chem. 1995,17,131-162. Reaction enthalpies in solution. Data included in the NIST Chemistry WebBook. 

Fig.7. A selection of organoruthenium complexes which display second harmonic generation and pyroelectric effects.

The Grubbs catalyst is an organoruthenium complex (Figure 17.10). The Grubbs reaction can be used in myriad ways with alkenes that contain many functional groups. It is one of the most important and widely used reactions in synthetic organic chemistry. 

Imidazole is characterized mainly by the T) (N) coordination mode, where N is the nitrogen atom of the pyridine type. The rare coordination modes are T) - (jt-) realized in the ruthenium complexes, I-ti (C,N)- in organoruthenium and organoosmium chemistry. Imidazolium salts and stable 1,3-disubsti-tuted imidazol-2-ylidenes give a vast group of mono-, bis-, and tris-carbene complexes characterized by stability and prominent catalytic activity. Benzimidazole follows the same trends. Biimidazoles and bibenzimidazoles are ligands as the neutral molecules, mono- and dianions. A variety of the coordination situations is, therefore, broad, but there are practically no deviations from the expected classical trends for the mono-, di-, and polynuclear A -complexes. 

The chemical reactivity of the organoruthenium and -osmium porphyrin complexes varies considerably, with some complexes (M(Por)R2, M(Por)R and Os(OEP)(NO)R) at least moderately air stable, while most are light sensitive and Stability is improved by handling them in the dark. Chemical transformations directly involving the methyl group have been observed for Ru(TTP) NO)Me, which inserts SO2 to form Ru(TTP)(N0) 0S(0)Me and Ru(OEP)Me which undergoes H- atom abstraction reactions with the radical trap TEMPO in benzene solution to yield Ru(OEP)(CO)(TEMPO). Isotope labeling studies indicate that the carbonyl carbon atom is derived from the methyl carbon atom. "" Reaction of... 

Organoruthenium and organoosmium compounds of polypyridine ligands offer alternative coordination modes of these ligands. In the cyclometalated complexes the ri (Ni, C2) coordination mode occurs. In some clusters the ri (Ni, C2) donor function is manifested. The latter becomes possible in clusters of 4,4 -bipyridine ligands, which otherwise play their traditional bridging function. 

The final chapter is a further installment in the ongoing series on the organic chemistry of heterocylic ligands in metallic complexes. The present contribution covers organoiron, organoruthenium, and organoosmium poly-pyridine complexes and is again authored by Alexander Sadimenko (Fort Hare University, Republic of South Africa). 

Williams, J.P. Bugarcic, T. Habtemariam, A. Giles, K. Campuzano, I. Rodger, P.M. Sadler, P.J., Isomer separation and gas-phase configurations of organoruthenium anticancer complexes ion mobility mass spectrometry and modeling, J. Am. Soc. Mass Spectrom. 2009, 20,1119-1122. 

Annual reviews have appeared of organoruthenium and -osmium chemistry in 1988, organoiron chemistry in 1989, and transition metals in hydroformylation, oxidation and reduction in 1989. The latest in an annual series of reviews on the mechanisms of inorganic reactions also contains much relevant material. 9 An analysis of the structural systemadcs of 1292 complexes with PK13 ligands has appeared. ... 

Organoruthenium compounds tend to form complexes coordinated by the 10 electrons of cyclic unsaturated compounds similar to ferrocene in organoiron compounds, for example, ruthenocene (r/ -C5H5)2Ru and tf( / -C6Hx)Ru. As shown in Scheme 16.1, ruthenium chloride 3H20 reacts with unsaturated cyclic compounds in the presence of zinc metal to afford cyclic compounds coordinated by 10 electrons by dehydrogenation [15-18]. In the case of cyclopentadiene, ruthenocene is formed by the coordination of two five-electron rings. In the case of 1,3-cyclohexadiene, the complex is obtained to be coordinated with 4-electron 1,3-cyclohexadiene and with 6-electron benzene. In the case of 1,3-cycloheptadiene... 

Organoruthenium compounds react with alkenes and alkynes to afford 7r-complexes as intermediates and addition reaction proceeds [74—79]. 

Wache, S. (1995) Organometallic complex catalysis in water. 2. Water-soluble organoruthenium(iv) catalysts for the emulsion polymerization of norbomene, J. Organomet. Chem., 494,235-40. 

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