Aryl complexes terminal ligands

Terminal ligands. Compounds of R3E(III)(E = As, Sb, Bi R = alkyl, aryl) are suitable for terminal n ligands the complex formation and donor capacity decrease in the sequence As > Sb > Bi, e.g. BiPh3 shows weak donor properties (see Section II.B). 

Photolysis of the carbodiimide complex 395 in hydrocarbon solvents similarly effects C H activation, via initial dissociation of the carbodiimide ligand to afford Tp Rh(CNCH2 Bu) as the active species. The reaction proceeds in a variety of neat aliphatic hydrocarbons, with apparently exclusive selectivity for the primary C H of terminal methyl groups. This includes the case of chloroalkanes, for which no oxidative addition of the C Cl bond is observed. Competition is, however, noted for aromatic substrates bearing methyl substituents, " with both benzylic and aromatic activation proceeding under kinetic control, though the aromatic activation products are thermodynamically favoured. Thus, toluene affords a kinetic mixture of aryl and benzyl complexes, which thermally redistributes to a 2 1 mixture of meta and para isomers of the aryl complex, while mesitylene yields a 3 1 mixture of the mesityl and benzyl complexes. 

Another family of phosphane ligands that contain a phosphine unit and stericaUy shielded nitrogen lone pairs in the ligand periphery are the so-called AZARYPHOS (aza-aryl-phosphane, L) ligands. The incorporation of these ligands into homoleptic ruthenium complexes [RuCp(L)2(MeCN)][PF6], either preformed [86] or generated in situ [87], provides catalysts for the anti-Markovnikov hydration of terminal... 

Table XI contains data for other organometallic complexes. The chloro complexes are of interest because they were reacted with terminal alkynes to afford alkynyl complexes, and the greater nonlinearity of the alkynyl complex eompared to the sum of the precursor alkyne and chloro complex suggests the importance of electronic communication between ligated metal and alkynyl ligand. The aryl complexes have a donor-bridge-acceptor composition, but nonlinearities are...

A palladium catalyst with a less electron-rich ligand, 2,2-dipyridyl-methylamine-based palladium complexes (4.2), is effective for coupling of aryl iodides or bromides with terminal alkynes in the presence of pyrrolidine and tetrabutylammonium acetate (TBAB) at 100°C in water.37 However, the reactions were shown to be faster in NMP solvent than in water under the reaction conditions. Palladium-phosphinous acid (POPd) was also reported as an effective catalyst for the Sonogashira cross-coupling reaction of aryl alkynes with aryl iodides, bromides, or chlorides in water (Eq. 4.18).38... 

Abstract This review describes recent results in the field of poly(aryleneethynylene)s (PAEs) that contain metal ions in the polymer backbone, or in the polymer side chain. This work is focused primarily on polymers possessing ligands of metal complexes as part of the aryle-neethynylene chain. PAEs with porphyrinylene in the backbone have also been addressed. Synthetic routes toward the polymers, as well as their photochemical, photophysical, and electrochemical properties, are presented. Monodisperse oligo(phenyleneethynylene)s with terminal metal complexes or with a ferrocene and thiol at each end are mentioned. 

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