A series of organonickel(II) complexes incorporating an amido phosphine ligand tethered with an amino pendant have been prepared and characterized. Deprotonation of N-(dimethylaminoethyl)-2-diphenylphosphinoaniline (H[PNN]) with one equivalent of n-BuLi in ethereal or hydrocarbon solutions at -35 °C generates cleanly dimeric {Li[PNN]}(2) as yellow crystals. The reaction of NiCl(2)(DME) with {Li...

Several routes for the synthesis of m-terphenyl thio-, seleno-, and telluroethers were investigated. m-Terphenyl iodides react with diphenyl diselenides or ditellurides (CsOH·H(2)O, DMSO, 110 °C) to give the desired compounds in 19-84% yield which significantly extends the previously reported such reactions because o-benzyne cannot be an intermediate as previously suggested. However, the most g...

Studying seemingly simple metathesis reactions between ZnCl(2) and (t)BuMgCl has, surprisingly, revealed a much more complex chemistry involving mixed magnesium-zinc compounds that could be regarded as Mg-Zn hybrids. Thus, the reaction of equimolar amounts of ZnCl(2) and (t)BuMgCl reveals the formation of the unprecedented mixed Mg-Zn complex [(THF)(4)Mg(mu-Cl)(2)Zn((t)Bu)(Cl)] (1), as a result...

Vanol is a member of the vaulted biaryl family of ligands and it has been proven to be very effective in a number of asymmetric catalytic reactions. The previous synthesis of vanol, while effective, is limited by the cost of reagents involved. The present work evaluates three different approaches to the synthesis of 3-phenyl-1-naphthol, a key intermediate in the synthesis of vanol. The first ap...

Nucleophilic addition to alkynes represents an attractive approach to the synthesis of olefins. Obstacles to this strategy include the low reactivity of alkynes toward many organometallic reagents and difficulties associated with controlling the regioselectivity of addition. Here we demonstrate that Fe(III) salts are effective precatalysts for the carbometalation of alkynes. Primary and seconda...