Arene complexes application

The University of Edinburgh (former employer of Peter J. Sadler) has filed patent applications relating to the ruthenium-arene, and platinum diazido complexes and University of Warwick for osmium-arene complexes under study in the Peter J. Sadler laboratory. 

Three types of reaction systems have been designed and applied for the enantioposition-selective asymmetric cross-coupling reactions so far. First example is asymmetric induction of planar chirality on chromium-arene complexes [7,8]. T vo chloro-suhstituents in a tricarhonyl("n6-o-dichlorobenzene)chromium are prochiral with respect to the planar chirality of the 7t-arene-metal moiety, thus an enantioposition-selective substitution at one of the two chloro substituents takes place to give a planar chiral monosubstitution product with a minor amount of the disubstitution product. A similar methodology of monosuhstitution can be applicable to the synthesis of axially chiral biaryl molecules from an achiral ditriflate in which the two tri-fluoromethanesulfonyloxy groups are enantiotopic [9-11]. The last example is intramolecular alkylation of alkenyl triflate with one of the enantiotopic alkylboranes, which leads to a chiral cyclic system [12], The structures of the three representative substrates are illustrated in Figure 8F.1. 

Bis(arene)chromium complexes applications, 5, 345 in engineered materials, 5, 344 Bis(arene) complexes... 

Bis( )6-arene)vanadium complexes applications, 5, 47 physical properties, 5, 47 reactivity, 5, 46 synthesis, 5, 45... 

Manganese carbenes, preparation, 5, 825 Manganese carbonyl complexes with 776-arene complexes, 5, 787 cyclopentadienyl complexes, 5, 783 with hydrocarbon ligands, complexes, 5, 776 synthesis and characteristics, 5, 761 Manganese carbonyl halides, applications and reactivity,... 

Complexes of Cr, W, Mo, Fe, Ru, V, Mn and Rh form stable, isolable arene if -complexes. Among them, arene complexes of Cr(CO)3 have high synthetic uses. When benzene is refluxed with Cr(CO)6 in a mixture of dibutyl ether and THF, three coordinated CO molecules are displaced with six-7r-electrons of benzene to form the stable i/fi-benzene chromium tricarbonyl complex (170) which satisfies the 18-electron rule (6 from benzene + 6 from Cr(0) + 6 from 3 CO = 18). Complex formation is facilitated by electron-donating groups on benzene, and no complex of nitrobenzene is formed. Complex formation has a profound effect on reactivity of arenes, and the resulting complexes are used in synthetic reactions. The metal-free reaction products can be isolated easily after decomplexation by mild oxidation using low-valent Cr. Cycloheptatriene also forms a stable complex with Cr(CO)3 and its synthetic applications are discussed below. 

Rigby J, Kondratenkov M (2004) Arene Complexes as Catalysts. 7 181-204 Rosch N (1999) A Critical Assessment of Density Functional Theory with Regard to Applications in Organometallic Chemistry. 4 109-163... 

Kiindig and coworkers have reported on the application of an azepine-derived lithium base 65 in the asymmetric desymmetrization of the carbamate arene complex 60... 

An interesting aspect is the application of these arene functionalised imidazolium salts as organometallic ionic liquids [139,142,143] whereby the imidazolium salt functions as the ionic liquid itself [139,143] or as the ionic liquid compatible part of the compound using the transition metal arene complex as a catalyst in biphasic applications [142],... 

Re arene complexes also result from application of the MVS technique to the extremely refractory Re metal (see Metal Vapor Synthesis of Transition Metal... 

Nazarov, A.A., Hartinger, C.G., Dyson, P.J. Opening the lid on piano-stool complexes an account of ruthenium(II)-arene complexes with medicinal applications. J. Organomet. Chem. 751, 251-260 (2014)... 

The widely applicable Fischer-Hafner method has been used to prepare arene complexes of most of the transition metals. The method involves the reaction of metal halide, aromatic hydrocarbon, aluminum trihalide, and aluminum metal, e.g. 53, 7576)(M = Cr, V),... 

Synthetic applications of the photochemistry of transition-metal arene complexes are rare, except for the (h -arene)M(CO)j (M = Cr, Mo, W) complexes where photo-substitution of ligands for CO occurs. These complexes also undergo arene exchange upon photolysis ... 

Applications of the photochemistry of isopropyl complexes include the synthesis of olefin and arene complexes through photolysis of (i-C3H,)jFe ... 

Water-soluble [60]fullerene-cationic homooxacalix[3]arene complex which is applicable to the photocleavage of DNA, A. Ikeda, T. Hatano, M. Kawaguchi, H. Suenaga and S. Shinkai, Chem. Commun., 1999, 1403. 

Abstract Methods of synthesis of i -arene complexes of Cr(CO)3, Mo(CO)3, Mn(CO)3, FeCp+, RuCp+ are reviewed. These electrophilic transition metal complex fragments have foimd application in arene transformations. Critical comparison of the routes of access is made and methods of decomplexation and where possible methods of recovery of the activating group are also detailed. Excluded from the overview are methods involving arene transformations in the coordination sphere of the metal. These wiU be contained in subsequent chapters. 

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