Enantioselective tandem alkylation/arylation of primary phosphines with 1-bromo-8-chloromethylnaphthalene catalyzed by Pt(DuPhos) complexes gave P-stereogenic 1-phosphaacenaphthenes (AcePhos) in up to 74% ee. Diastereoselective formation of four P-C bonds in one pot with bis(primary) phosphines gave C2-symmetric diphosphines, including the o-phenylene derivative DuAcePhos, for which the rac isomer was formed with high enantioselectivity. These reactions, which appear to proceed via an unusual metal-mediated nucleophilic aromatic substitution pathway, yield a new class of heterocycles with potential applications in asymmetric catalysis.

The synthetic strategies, structural comparison, and thermal gravimetric analyses for a novel family of alkaline earth metal perfluoro-tert-butoxides (PFTB) are presented. The isolated complexes follow the general formula, [Ae(PFTB)(2)(d)(x)]; (1a, Ae = Mg, d = THF, x = 2; 1b, Ae = Ca, d = THF, x = 4; 1c, Ae = Sr, d = THF, x = 4; 1d, Ae = Ba, d = THF, x = 4; 2a, Ae = Mg, d = DME, x = 1; 2b, Ae = Ca, d = DME, x = 2; 2c, Ae = Sr, d = DME, x = 2; 2d, Ae = Ba, d = DME, x = 3; 3a, Ae = Mg, d = diglyme, x = 1; 3b, Ae = Ca, d = diglyme, x = 2; 3c, Ae = Sr, d = diglyme, x = 2; 3d, Ae = Ba, d = diglyme, x = 2; THF = tetrahydrofuran, DME = 1,2-dimethoxyethane) where the crystallographically characterized compounds display either a cis or trans conformations in octahedral or pseudo-octahedral environments. Alkane elimination (Mg), direct metalation via ammonia activation (Ca, Sr, Ba), and transamination (Ca, Sr, Ba) methods yielded the target compounds in moderate to good yields. Structural studies of select compounds showed all compounds to be monomeric with varying degrees of co-ligand coordination, possibly explaining some of the observed physical properties. Thermal gravimetric analyses of the compounds shows sublimation at low temperatures, associated with minimal residue, making this family of fluoroalkoxides promising candidates for metal organic chemical vapor deposition (MOCVD).

Four novel alkaline earth metal tetranuclear aryloxide/pyrazolate hydroxides of the general formula M4(ligand)6(OH)2(donor)n have been prepared by either adding stoichiometric quantities of water to preformed alkaline earth metal aryloxides or in a direct metalation regime combining metal, ligand (alcohol, pyrazole), and donor with stoichiometric amounts of water. The compounds are considered as potential intermediates in the sol-gel process. A nonhydrolyzable magnesium aryloxide has also been obtained using the same reaction scheme. Unexpectedly, a dimeric strontium complex with further association of a second dimer via hydrogen bonding from the solvent of crystallization, ethylenediamine, has been isolated by the treatment of strontium metal with a mixture of alcohol and water. All compounds were characterized using X-ray crystallography, 1H and 13C NMR, and IR spectroscopy.