Five-Coordinate Platinum(II) Compounds Containing Sugar Ligands: Synthesis, Characterization, Cytotoxic Activity, and Interaction with Biological Macromolecules.

This article describes the synthesis and characterization of novel cationic five-coordinate Pt(II) complexes containing nitrogen sugar-based ligands. The cytotoxicity of the complexes was evaluated on different cell lines with the expectation that both the coordinative saturation and the sugar moiety cooperate to enhance their biological activity. In fact, the complexes resulted to be more active than cisplatin but still with little selectivity. They activate the apoptosis pathway. Binding of representative compounds with DNA was studied by ethidium bromide displacement assay and circular dichroism. Binding to model proteins was also investigated; the X-ray structure of the adduct formed in the reaction between a representative compound and the model protein bovine pancreatic ribonuclease was obtained. The structure discloses an unprecedented interaction between a five-coordinate Pt(II) moiety and a His side chain.

Unexpected anion effect in the alkoxylation of alkynes catalyzed by N-heterocyclic carbene (NHC) cationic gold complexes.

The intermolecular alkoxylation of alkynes is the oldest application of cationic gold(I) catalysts; however, no systematic experimental data about the role of the anion are available. In this contribution, the role of the anion in this catalytic reaction as promoted by a N-heterocyclic carbene-based gold catalyst, [(NHC)AuX] (X=BARF(-) , BF4 (-) , OTf(-) , OTs(-) , TFA(-) , or OAc(-) ) is analyzed, through a combined experimental (NMR spectroscopy) and theoretical (DFT calculation) approach. The most important factor seems to be the ability to abstract the proton from the methanol during the nucleophilic attack, and such ability is related to the anion basicity. On the other hand, too high coordination power or basicity of the anion worsens the catalytic performance by preventing alkyne coordination or by forming too much free methoxide in solution, which poisons the catalyst. The intermediate coordinating power and basicity of the OTs(-) anion provides the best compromise to achieve efficient catalysis.

Unique syndio-selectivity in CO/styrene copolymerization reaction catalyzed by palladium complexes with 2-(2'-oxazolinyl)-1,10-phenanthrolines.

The reaction of the neutral Pd complex [Pd(CH(3))Cl(cod)] with the potentially terdentate 2-oxazolinyl phenanthroline ligands 1-3 affords the corresponding cationic dinuclear Pd-complexes 1a-3a, which can be isolated in the solid state in good yields. By treatment with AgPF(6) the complexes 1a-3a were converted into the corresponding hexafluorophosphate derivatives 1b-3b, where both the ligand units feature a terdentate coordination around the two Pd-centres with the phenanthroline fragment of each unit displaying a chelate coordination to one Pd-centre, while the corresponding oxazolinyl pendant acts as a bridging ligand towards the second Pd-centre. The persistence of this dimeric structure of 1b-3b in CD(2)Cl(2) solution was confirmed by (15)N-NMR experiments at natural abundance, which clearly show the binding to the metal of all of the nitrogen donors, as well as the overall C(2) symmetry of the compound. In consequence of the different strengths of the relevant ion-pair, the dimeric structure of the complex undergoes partial fragmentation in the case of the chloride derivatives 1a-3a, as evidenced from the (15)N-NMR spectra. Complexes 1b-3b are active catalysts in styrene alternate carbonylation, where, under very mild conditions (30 °C and 1 atm of CO), they provide oligomers with 3-5 repetitive units as the exclusive or prevailing product. When traces of the CO/styrene polyketones are also formed, their (13)C-NMR characterization shows that they are stereochemically homogeneous with a unique syndio-tacticity. This result implies that Pd-complexes able to induce a complete enantioface discrimination in the insertion step of the alkene during the catalytic cycle of the styrene alternate carbonylation have been produced for the first time.