Arene complexes nucleophilic addition

Semmelhack MF (1995) Transition metal arene complexes nucleophilic addition. In Abel EW, Stone FGA, Wilkinson G (eds) Comprehensive organometallic chemistry II. Pergamon, Oxford New York Tokyo, Sect 9.1... 

Activation of aromatic compounds by transition-metal complexes was initially studied with Cr(CO)3 complexes. Nucleophilic addition of 2-lithio-l,3-dithianes to arene-chromium(O) complexes 185 followed usually by iodine-promoted decomplexation affords the corresponding 2-arylated 1,3-dithianes 186. The reaction of //-(toluene)- and (anisole)tricarbonylchromium (185) with compound 161 gave mixtures (52 46 and 10 90, respectively) of ortho and meta substituted derivatives (186) (Scheme 54)244. The meta directing effect was also observed (mainly better than 95%) with amino and fluoro substituted complexes245. 

Addition of Oxygen Nucleophiles to Transition Metal 7r-Arene Complexes 685... 

Neutral (cyclohexadienyl)manganese complexes 71, generated by nucleophilic addition to (arene)Mn(CO)3+ cations 65, undergo ligand substitution with nitrosyl hexafluorophosphate to give the corresponding (cyclohexadienyl)Mn(CO)2NO+ cations 72 (Scheme 17)93. Attack by a wide variety of nucleophiles on cations 72... 

The first arene-transition metal complexes were prepared in the 1950s1314 and it was immediately recognized that the added polarizibility or electron deficiency would promote addition of nucleophiles to the arene ligand. A number of cyclohexadienyl complexes were characterized following nucleophilic addition, but the question of inducing the ipso hydrogen to depart was not answered (equation 1). 

The intermediate iis-cyclohexadienyl anionic species from nucleophilic addition to the [(arene)Cr(CO)3] complexes are obviously highly electron rich and should be susceptible to reactions... 

The deoxygenation of arene oxides have also been achieved by using chromium carbonyl complexes. The aromatic hydrocarbons produced are partially converted to chromium complexes. Formation of 246 in methanol suggests Rh-catalyzed solvolysis, resulting in nucleophilic addition of meth-... 

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