Reactions of neodymium(II) iodide with organohalides

Abstract The reactions of NdI 2 ( 1 ) with aryl halides, PhX (X = Cl, Br, I), in THF afford benzene and a minor amount of biphenyl. Benzyl chloride under the same conditions yields 1,2-diphenylethane, toluene and PhCH 2 I due to Cl/I exchange. Alkyl halides C 7 H 15 Br and cyclo -C 6 H 11 Cl are reduced to the corresponding hydrocarbons. t -BuCl affords a mixture of isobutane/isobutylene. Chlorotrimethylsilane is converted into Me 3 SiH, hexamethyldisilane and Me 3 SiO(CH 2 ) 4 CH 3 in 10%, 8% and 31% yields respectively at room temperature but 1%, 2% and 88% yields at −60 °C. In benzene, the interaction of 1 with benzyl chloride proceeds at 80 °C to give diphenylmethane in 66% yield. Without solvent the same reaction leads to formation of the oligomers PhCH 2 ( p -C 6 H 4 CH 2 ) n C 6 H 4 CH 2 Cl. Heating 1 in benzene with n -BuCl or cyclo -C 6 H 11 Cl affords mono- and disubstituted products, RC 6 H 5 and 1,4-R 2 C 6 H 4 . The n -Bu groups in the reaction transform into sec -Bu isomers. Iodobenzene, bromobenzene, Me 3 SiCH 2 Cl and Me 3 SiCl are inert towards 1 in benzene.