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The Grignard reagent ArF′MgBr (ArF′ = 4-(C6F5)C6F4) reacts with Me3SiCl, Me2SiCl2and 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 BF3was not selective, while one equivalent of ArF′MgBr and (ArF)2BF (ArF= C6F5) reacted cleanly to give (ArF)2ArF′B. Treatment of BCl3with 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·OH2as a hydrogen-bonded dimer. The Grignard reagent reacts selectively with ZnCl2in diethyl ether giving first [(ArF′)Zn(μ-Cl)(OEt2)]2then (ArF′)2Zn(OEt2)2, both of which have been characterised by X-ray diffraction. The corresponding reaction with HgCl2requires the use of tetrahydrofuran as the solvent and yields (ArF′)2Hg(THF)2. [ABSTRACT FROM AUTHOR]

The ammonia adduct of tris(pentafluorophenyl)boron, (C6F5)3B·NH3, is a potentially tri-functional hydrogen-bond donor. Co-crystallisation with the bases acetonitrile, pyridine, tetrahydrofuran, tetramethylethylenediamine, 15-crown-5, 1,4-diazabicyclo[2.2.2]octane (DABCO), pyrazine and 4,4′-bipyridine results, not in donor exchange, but in the formation of supermolecules assembled through hydrogen bonding to second coordination sphere acceptors. The complexes have been characterised by elemental analysis, multinuclear NMR and single-crystal diffraction methods. The solid-state architectures range in complexity, from the hydrogen bonded pairing of (C6F5)3B·NH3, with a single monodentate acceptor molecule (e.g.MeCN to form (C6F5)3B·NH3·NCMe), through complexation with all three N–H groups to the macrocycle 15-crown-5, to the formation of infinite one-dimensional chains with pyrazine and DABCO, and to two-dimensional networks with the divergent acceptor 4,4′-bipyridine. [ABSTRACT FROM AUTHOR]

Treatment of Cp2HfCl2with two equivalents of LiNH2BH(C6F5)2in toluene solution yields Cp2Hf{NHBH(C6F5)2}, which has been crystallographically characterised. The otherwise base-free [NHBH(C6F5)2] complex is stabilised by an agostic interaction. [ABSTRACT FROM AUTHOR]

The crystalline ion-pair [TiCl(NMe2)2(NMe2H)2]+[TiCl2{NB(C6F5)3}(NMe2H)2]−, in which the anion has a triply bonded nitridoborate ligand, is formed through the multiple activation of H3N·B(C6F5)3when treated with [Ti(NMe2)3Cl]. [ABSTRACT FROM AUTHOR]