Halides as ligand

In naming ligands, an o is added to the root name of an anion. For example, the halides as ligands are called fluoro, chloro, bromo, and iodo hydroxide is hydroxo and cyanide is cyano. For a neutral ligand the name of the molecule is used, with the exception of H20, NH3, CO, and NO, as illustrated in Table 20.14. 

Chiral oxazolines developed by Albert I. Meyers and coworkers have been employed as activating groups and/or chiral auxiliaries in nucleophilic addition and substitution reactions that lead to the asymmetric construction of carbon-carbon bonds. For example, metalation of chiral oxazoline 1 followed by alkylation and hydrolysis affords enantioenriched carboxylic acid 2. Enantioenriched dihydronaphthalenes are produced via addition of alkyllithium reagents to 1-naphthyloxazoline 3 followed by alkylation of the resulting anion with an alkyl halide to give 4, which is subjected to reductive cleavage of the oxazoline moiety to yield aldehyde 5. Chiral oxazolines have also found numerous applications as ligands in asymmetric catalysis these applications have been recently reviewed, and are not discussed in this chapter. ... 

Many Cu(I) compounds have polymeric structures with weak Cu—Cu bonds that are bridged by atoms or groups. These include Cu(I) carboxylates, alkyls and aryls, alkoxides and (CuXL) complexes (X = halide, L = ligand). In Cu(I) compounds Cu has a filled 3d shell, 3d , that does not participate in metal-metal bonding, so the extent of metal-metal bonding in these compounds is questionable. Calculations show that the metal-metal bonding is at best weak . These compounds arise from the same syntheses as would be used to prepare the monomer, and so they are not considered further here. 

Substituted thioureas have been extensively studied over the decades. Reaction of CoX2 (X = C1, Br) with substituted phenylthioureas yield a range of complexes involving halide and thiourea as ligands, characterized by spectroscopy and thermogravimetric analysis.503 Both [Co(Rtu)4(OH2)2]2+ (Rtu = thiourea, phenylthiourea, allylthiourea) and [Co(Rtu)2(OH2)4]2+ (Rtu = diphenylthiourea) have been prepared and characterized as low-spin octahedral species.504 The octahedral bis(phenylthiourea)bis(dithiolate)cobalt(II) complex, one of a number of complexes of phenylthiourea, chlorophenylthiourea and bis(diphenylphospinothioyl)methane prepared and characterized,505 proved the most biologically active of those tested. 

Novel catalytic systems, initially used for atom transfer radical additions in organic chemistry, have been employed in polymer science and referred to as atom transfer radical polymerization, ATRP [62-65]. Among the different systems developed, two have been widely used. The first involves the use of ruthenium catalysts [e.g. RuCl2(PPh3)2] in the presence of CC14 as the initiator and aluminum alkoxides as the activators. The second employs the catalytic system CuX/bpy (X = halogen) in the presence of alkyl halides as the initiators. Bpy is a 4,4/-dialkyl-substituted bipyridine, which acts as the catalyst s ligand. 

In addition, complexes of P(/-Bu)3 have been shown to catalyze the formation of diaryl heteroarylamines from bromothiophenes.224 Aminations of five-membered heterocyclic halides such as furans and thiophenes are limited because their electron-rich character makes oxidative addition of the heteroaryl halide and reductive elimination of amine slower than it is for simple aryl halides. Reactions of diarylamines with 3-bromothiophenes occurred in higher yields than did reactions of 2-bromothiophene, but reactions of substituted bromothiophenes occurred in more variable yields. The yields for reactions of these substrates in the presence of catalysts bearing P(/-Bu)3 as ligand were much higher than those in the presence of catalysts ligated by arylphosphines. 

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