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An unprecedented pentanuclear lanthanum thiolate oxide complex is isolated as a result of the adventitious water but is regenerated in an acceptable yield through control of hydrolysis. This synthetic strategy can be used in the preparation of other new oxolanthanide thiolate complexes with better catalytic performances.

A palladium-catalyzed tandem C-H activation/biscyclization reaction of propargylic carbonates with terminal alkynes is determined, which has allowed the tetracyclic benz[a]anthracene framework to be built with high regioselectivity. A possible mechanism is discussed for this tandem C-H activation/biscyclization process.

A general protocol is developed for the rhodium-catalyzed oxidative carbonylation of arenes to form esters, which has used a directed C-H bond activation coupled with a benign terminal oxidant. The studies have shown that Oxone has played a key role in the transformation.

The effects of ligand symmetry on the rational design and construction of Mo/Cu/S cluster-based supramolecular arrays are analyzed. The results have shown that the formation of the four different multidimensional topological structures is affected by the symmetry of the multitopic ligands.

A set of new [W[S.sub.4][Cu.sub.4]]- or [MoO[S.sub.3][Cu.sub.3]-based supramolecular assemblies are prepared from reactions of preformed cluster compounds [[[Et.sub.4]N].sub.4][W[S.sub.4][Cu.sub.4][I.sub.6]] and [[[(n-Bu).sub.4]N].sub.2][MoO[S.sub.3][Cu.sub.3][X.sub.3] (X = I, SCN) with flexible ditopic ligands. The results have provided new routes to the rational design and construction of complicated cluster-based supramolecular arrays.

A route to construction of two tetranuclear metal string compounds [{[[(Tab).sub.2]Ag][Au[(CN).sub.2]]}.sub.2] and [{[[(Tab).sub.2]Ag][Au[(CN).sub.2]]}.sub.2] from reactions of preformed complexes [[Au[(Tab).sub.2]].sub.2][([PF.sub.6]).sub.2] and [Ag[(Tab).sub.2]]([PF.sub.6])with K[Au[(CN).sub.2]] is demonstrated. These did not show luminescence, because these compounds, when dissolved tend to dissociate into nonemissive monomeric species, in which ionic interactions and aurophilic bonding interactions are not present.

Approaches to assembly of [[[eta.sup.5]-[C.sub.5][Me.sub.5]]W[S.sub.3][Cu.sub.3]]-based supramolecular compounds from pre-formed incomplete cubane-like clusters [P[Ph.sub.4]][[eta.sup.5]-[C.sub.5][Me.sub.5]]W[S.sub.3][Cu[X.sub.3]] (X=CN, Br) is investigated. The successful construction of compounds from the geometry-fixed clusters expands the scope of the rational design and construction of cluster-based supramolecular assemblies.

Hg(OAc)2 reacts with TabHPF6 [TabH=4-(trimethylammonio)benzenethiol] in MeCN/MeOH to form a mononuclear linear complex [Hg(tab)2](PF6)2. By using this complex as precursor, a new family of mercury(II) zwitterionic thiolate complexes, are prepared and characterized by elemental analysis, IR spectra, UV-vis spectra, H NMR and single-crystal X-ray crystallography.

The introduction of Li(super +) and Cl(super -) ions into lanthanide amide complexes afforded three unprecedented Ln-thiolate compounds when treated with a low concentration of benzenthiol. It is anticipated that the synthetic methodology might be applied to other Ln-amide compounds to yield previously unknown species with better catalytic activities.