The synthesis, structure and reactivity of 4-nonafluorobiphenyl complexes.
The Grignard reagent Ar(F)'MgBr (Ar(F)' = 4-(C(6)F(5))C(6)F(4)) reacts with Me(3)SiCl, Me(2)SiCl(2) and Me(3)SnCl to give the 4-nonafluorobiphenyl group 14 complexes Ar(F)'Me(3)Si, (Ar(F)')(2)Me(2)Si and Ar(F)'Me(3)Sn respectively. Ar(F)'Me(3)Sn undergoes only methyl group exchange when treated with BBr(3), yielding Ar(F)'Me(2)SnBr. The solid state structures of Ar(F)'Me(3)Sn and Ar(F)'Me(2)SnBr have been determined and exhibit the expected distorted tetrahedral geometries at tin. The reaction between three equivalents of Ar(F)'MgBr and BF(3) was not selective, while one equivalent of Ar(F)'MgBr and (Ar(F))(2)BF (Ar(F) = C(6)F(5)) reacted cleanly to give (Ar(F))(2)Ar(F)'B. Treatment of BCl(3) with three equivalents of Ar(F)'Li, prepared at low temperature from the reaction between Ar(F)'Br and n-BuLi, yielded (Ar(F)')(3)B. The molecular structures of the acetonitrile adducts of (Ar(F))(2)Ar(F)'B and (Ar(F)')(3)B closely resemble that of (Ar(F))(3)B.NCMe. During the course of the boron investigations, reaction with adventitious water led to the structural characterization of (Ar(F)')(2)BOH.OH(2) as a hydrogen-bonded dimer. The Grignard reagent reacts selectively with ZnCl(2) in diethyl ether giving first [(Ar(F)')Zn(micro-Cl)(OEt(2))](2) then (Ar(F)')(2)Zn(OEt(2))(2), both of which have been characterised by X-ray diffraction. The corresponding reaction with HgCl(2) requires the use of tetrahydrofuran as the solvent and yields (Ar(F)')(2)Hg(THF)(2).
Wolfson Materials and Catalysis Centre, School of Chemical Sciences and Pharmacy, University of East Anglia, Norwich, UK.
Eddy
E
Martin
David L
DL
Hughes
Michael B
MB
Hursthouse
Louise
L
Male
Simon J
SJ
Lancaster