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Novel water-soluble Cp*Ir-am ine complexes are prepared and a new highly atom-economical system for the preparation of organic amines by using aqueous ammonia as a nitrogen source is developed. A water-soluble and air-stable Cp*Ir-ammine catalyst is used for preparing a variety of tertiary and secondary amines by the multialkylation of aqueous ammonia with theoretical equivalents of primary and secondary alcohols.

Ni/P[(c-[C.sub.5][H.sub.9]).sub.3] (P[Cyp.sub.3]) catalyst is highly effective for direct alkenylation and alkylation of polyfluoroarenes by using C-H activation followed by the insertion of alkynes, 1,3-dienes and vinylarenes. The origin of the dramatic ligand effect on the Ni catalysis for C-H activation of polyfluororenes and the development of other C-H functionalizations of E-containing substrates via Ni catalysis are discussed.

An alkylation of aminals with organozinc reagents derived from allyl bromide, benzyl amide, [alpha]-bromoacetate and [alpha]-bromonitrile is carried out in the presence of TMSCl and diisopropylamine. This reaction system is applied to the preparation of an antispasmodic, butaverine.

Alkylation of zinc-bound thiolates has occurred in both catalytic and structural zinc sites of enzymes. A dianionic complex has followed a dissociative pathway, whereas an associative one is preferred for a neutral system.

The synthesis and structural characterization of alkylated [Ln.sup.II]-[Al.sup.III] heterometallic aryloxide complexes are described. The new homo- and heteroleptic aryloxide complexes in absence of any donor solvent molecules are stereoelectronically unsaturated and feature distinct secondary intramolecular interactions.

The hydrogallation reaction of trimethylsilylethynylbenzenes with the hydridodichlorogallium compound H-Ga[Cl.sub.2] is used to obtain the alkenylphenyl compounds of [C.sub.6][H.sub.6-x][[C(H)=C(Si[Me.sub.3])-Ga[Cl.sub.2]].sub.x] [x = 1 to 3]. The compounds contain up to three Ga[Cl.sub.2] groups, which could find application in alkylation reactions by salt elimination.

Five new pseudotetrahedral nickel(II) arylthiolate complexes are prepared by metathesis reactions of known chloride complexes with sodium arylthiolate salts in THF. The reactivity of the nickel-thiolate linkage toward electrophilic alkylation with MeI is affected, indicating increased rates according to two distinct competing mechanisms, direct biomolecular alkylation of intact complex and rate-limiting unimolecular dissociation of free thiolate.

An efficient method is developed for catalytic asymmetric allylic alkylations (AAA) with vinylaluminum reactions of commercially available DIBAL-H with readily accessible terminal alkynes efficiently deliver the vinylmetals. The catalytic AAA reactions involving vinylmetal reagents are described.