The Grignard reagent ArF'MgBr (ArF' = 4-(C6F5)C6F4) reacts with Me3SiCl, Me2SiCl2 and Me3SnCl to give the 4-nonafluorobiphenyl group 14 complexes ArF'Me3Si, (ArF')2Me2Si and ArF'Me3Sn respectively. ArF'Me3Sn undergoes only methyl group exchange when treated with BBr3, yielding ArF'Me2SnBr. The solid state structures of ArF'Me3Sn and ArF'Me2SnBr have been determined and exhibit the expected distorted tetrahedral geometries at tin. The reaction between three equivalents of ArF'MgBr and BF3 was not selective, while one equivalent of ArF'MgBr and (ArF)2BF (ArF = C6F5) reacted cleanly to give (ArF)2ArF'B. Treatment of BCl3 with three equivalents of ArF'Li, prepared at low temperature from the reaction between ArF'Br and n-BuLi, yielded (ArF')3B. The molecular structures of the acetonitrile adducts of (ArF)2ArF'B and (ArF')3B closely resemble that of (ArF)3B·NCMe. During the course of the boron investigations, reaction with adventitious water led to the structural characterization of (ArF')2BOH·OH2 as a hydrogen-bonded dimer. The Grignard reagent reacts selectively with ZnCl2 in diethyl ether giving first [(ArF')Zn(µ-Cl)(OEt2)]2 then (ArF')2Zn(OEt2)2, both of which have been characterised by X-ray diffraction. The corresponding reaction with HgCl2 requires the use of tetrahydrofuran as the solvent and yields (ArF')2Hg(THF)2.
|Number of pages||9|
|Publication status||Published - 19 Jan 2009|