Cycloruthenated complex

Very recently, Parkhomenko et al. used cycloruthenated complexes 155a and 155b to catalyze the Kharasch addition of Cl3CBr to styrene, methyl methacrylate, acrylate, and 1-hexene in high yields [226]. The reaction with CC14, on the other hand, required microwave irradiation for all complexes and substrates to achieve moderate to good yields. 

The cycloruthenation of substituted A, A -dimethylbenzylamines by [77°-C6H6)RuCl( t-Cl)]2 in acetonitrile in the presence of NaOH and KPp6, which led to the formation of corresponding cycloruthenated complexes in good to moderate yields, has also been studied <1999OM2390>. For example, the work of Le Lagadec and co-workers is illustrated in Equation (17) <2004JOM4820>. As shown in Equation (17), the cycloruthenation of the 3-substituted A, A -dimethylbenzylamine 69 afforded two positional isomers as a result of the Ru(li) attack at the G-2 or C-6 aromatic carbons. 

Several cycloruthenated complexes have been prepared and characterized, but no comparison can be made with the development of Ru(II)-polypyridine chemistry. This is even more true as far as luminescence is concerned hundreds of luminescent Ru(II) polypyridine complexes have been investigated [15], whereas only a few luminescent cycloruthenated complexes have been reported. 

The cyclometalated Ru species generated electrochemically are very reactive in oxidation of reduced flavin adenine dinucleotide of GO. The excellent coupling between GO reduced by D-glucose and the Ru species is illustrated by the rate constant for the complex [Ru(phpy)(Me2phen)2]PF6, which equals 1.8x10 M s at pH 6.7 and 25 °C. There are no complexes of higher reactivity in Table VII Other cycloruthenated complexes are very reactive as well (Table IX). Variation of the nature of cycloruthenated and diimine... 

When the C-H activation process is inefficient or difficult to carry out, one can often resort to alternative methods such as transmetallation reactions, as in the synthesis of the interesting cycloruthenated complex 13. The corresponding C-H activation process for 2 gives only a 38% yield." A similar method was employed for the synthetically useful cyclopalladated ketone derivative 15 and for the organomolybdenum complex 17.Oxidative additions of suitably substituted iodo derivatives on Pd(0) were employed to synthesize the primary 8-napthylamine complex 19 and the complexes 21 with a variety of substitution patterns on the thioether group. 

The cycloruthenated complex 13 reacts with disubstituted alkynes to afford the novel Ti -aiene Ru(0) complexes 49 which were isolated, characterized by X-ray methods, and oxidatively demetallated by treatment with Cu(II) salts to afford metal-free(7i0"isoquinolium salts 43 (with PF as counterion). Kinetic studies have revealed that the reaction proceeds via insertion of the alkyne into the Ru-C bond and that for this process the rate-limiting step is very similar to that found for the analogous palladium compound. Irradiation or thermal treatment of the cycloruthenated complex 50 with diphenylacetylene yields diphenylindole 51 as product. A similar reaction is observed with the corresponding iron or molybdenum complexes. ... 

Insertion reactions of unsaturated organic substrates into the Ru-G bond of aryl-cycloruthenated complexes have been reported. Thus, alkenyl-type derivatives 285 (Figure 40) have been synthesized by reacting ruthenacycles... 

Synthesis of cycloruthenated pyrido[2,3-fl]pyrrolo[3,4-c]carbazole-5,7(6H)-diones and ruthenium complexes as protein kinase inhibitors 07SU177. 

A cycloruthenated amine complex, depicted in Scheme 4.26, was successfully applied by Arends s group to promote the DKR of phenylethanol." The reaction was performed with CAL-B in the presence of isopropyl acetate and t-BuOK, providing the corresponding enantiopure acetate in good yield. 

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