Well-defined alkylpalladium complexes with pyridine-carboxylate ligands as catalysts for the aerobic oxidation of alcohols.

Neophylpalladium complexes of the type [Pd(CH(2)CMe(2)Ph)(N-O)(L)], where N-O is picolinate or a related bidentate, monoanionic ligand (6-methylpyridine-2-carboxylate, quinoline-2-carboxylate, 2-pyridylacetate or pyridine-2-sulfonate) and L is pyridine or a pyridine derivative, efficiently catalyze the oxidation of a range of aliphatic, benzylic and allylic alcohols with oxygen, without requiring any additives. A versatile method is described which allows the synthesis of the above-mentioned complexes with a minimum synthetic effort from readily available materials. Comparison of the rates of oxidation of 1-phenylethanol with different catalysts reveals the influence of the structure of the bidentate N-O chelate and the monodentate ligand L on the catalytic performance of these complexes.

Selective reduction of a Pd pincer PCP complex to well-defined Pd(0) species.

Well-defined dimeric or polymeric Pd(0) complexes [Pd(µ-(iPr)PCHP)](n) (n = 2 or ∞) containing the bridging ligand α,α'-bis(diisopropylphosphino)-m-xylene ((iPr)PCHP) are produced under mild conditions when the cyclometallated PCP pincer complex ((iPr)PCP)Pd-OH reacts with methanol or isopropanol.

Structural characterization and bonding properties of lithium naphthalene radical anion, [Li+(TMEDA)2][C10H8(*-)], and lithium naphthalene dianion [(Li+TMEDA)2C10H8(-)2].

The crystal structures of lithium naphthalene radical-anion (LiC10H8) and lithium naphthalene dianion (Li2C10H8) are reported, and their bonding properties analyzed.

New modes of reactivity in the threshold of the reduction potential in solution. Alkylation of lithium PAH (polycyclic aromatic hydrocarbon) dianions by primary fluoroalkanes: a reaction pathway complementing the classical birch reductive alkylation.

Some of the most highly reduced organic species in solution, such as the dianions of PAHs (polycyclic aromatic hydrocarbons) display unexpected reactivity patterns when they react with an appropriate counterpart. As seen before in their reaction with propene and other alkenes, PAHs(-2) apparently react with fluoroalkanes in a nucleophilic fashion in spite of being generally regarded as powerful electron-transfer reagents in their reactions with haloalkanes. This methodology complements the current methodologies on reductive alkylation of polycyclic arenes by allowing access to a new set of regioisomers, the regiochemistry of which can be easily predicted by simple MO calculations.