The hydroauration of internal and terminal alkynes by gold(III) hydride complexes [(C^N^C)AuH] was found to be mediated by radicals and proceeds by an unexpected binuclear outer‐sphere mechanism to cleanly form trans‐insertion products. Radical precursors such as azobisisobutyronitrile lead to a drastic rate enhancement. DFT calculations support the proposed radical mechanism, with very low activation barriers, and rule out mononuclear mechanistic alternatives. These alkyne hydroaurations are highly regio‐ and stereospecific for the formation of Z‐vinyl isomers, with Z/E ratios of >99:1 in most cases.

Four new fluorescent chemosensors for metal ions based on 8-hydroxyquinoline (8-HDQ) derivatives and sulfur-containing macrocyclic units were synthesized and characterized, namely 1-(5-chloro-8-hydroxy-7-quinolinylmethyl)-1-aza-4,7,10-trithiacyclododecane (L1), 1-(5-chloro-8-hydroxy-7-quinolinylmethyl)-1-aza-4,13-dithia-7,10-dioxacyclopentadecane (L2), 1-(8-hydroxy-2-quinolinylmethyl)-1-aza-4,7,10-trithiacyclododecane (L3), and 1-(8-hydroxy-2-quinolinylmethyl)-1-aza-4,13-dithia-7,10-dioxacyclopentadecane (L4). Preliminary fluorimetric titrations indicated L1 as the only member of the family of ligands to give a selective CHEF-type response to the presence of Zn²⁺ in MeCN–H₂O (1 : 1, v/v) solutions, which allowed imaging of this metal ion in Cos-7 cells in vitro. The other ligands either did not show any fluorescence response (L3, L4) to any of the metal ions considered (Cu²⁺, Zn²⁺, Cd²⁺, Hg²⁺ and Pb²⁺) or gave (L2) a CHEF-type response also to the presence of Cd²⁺. The coordination properties of L1 towards Zn²⁺ were, therefore, fully investigated by potentiometric measurements and absorption and emission spectroscopy at different pH values, which indicated that the formation of 2 : 1 L1/Zn²⁺ complexes is responsible for the CHEF-type effect observed. The complexes [Zn(L1)₂H₂O](BF₄)₂ and [Zn(L3)](ClO₄)₂ were characterized in the solid state by X-ray crystallography, and DFT calculations were performed to understand the origin of the Zn²⁺/Cd²⁺ optical discrimination of the 8-HDQ-based “conjugate” fluorescent chemosensors reported.

Proceeding from a ligand constituted by two units of kojic acid linked by a methylene group, which proved a very promising chelator for excess iron(III) and aluminium(III) pathologies, two new ligands have been designed and synthesized: one by adding a vanillin molecule in the linker and the second by adding an o-vanillin molecule. Both these ligands, on the basis of complex formation studies presented here, show significant potential as therapeutic agents for iron and aluminium overload. Protonation constants of the pure ligands have been determined by potentiometry, and standard reaction heats by calorimetry. Hydrogen bonding plays an important role in the protonation reactions. The crystal structures of both ligands have furthermore been resolved. Complex formation equilibria for the iron complexes have been studied by combined potentiometry–spectrophotometry and those of aluminium by potentiometry alone. All complexes were found to contain two metal ions. NMR diffusion measurements hardly applied to complex formation equilibria and the results of density functional theory (DFT) calculations were powerful tools in confirming the proposed reaction model and in evaluating the relative stabilities of the products. Further support was given by NMR chemical shift measurements and electrospray mass spectrometry.

The synthesis of 5-hydroxy-2-(hydroxymethyl)pyridin-4(1H)-one (P1) is presented, together with the evaluation of its coordination ability towards Fe³⁺, studied by a combination of chemical, computational, and animal approaches. The use of complementary analytical techniques has allowed us to give evidence of the tautomeric changes of P1 as a function of pH, and to determine their influence on the coordinating ability of P1 towards Fe³⁺. The pFe³⁺ value 22.0 of P1–iron complexes is noticeably higher than that of deferiprone (20.6), one of the three clinical chelating agents in therapeutic use for iron overload diseases. This is due on one side to the tautomeric change to the catechol form, and on the other to the lower protonation constant of the OH group. Bio-distribution studies on mice allowed us to confirm in vivo the efficacy of P1. Furthermore the coordinating ability toward Al³⁺, Cu²⁺ and Zn²⁺ has been studied to evaluate the possible use of P1 against a second toxic metal ion (Al³⁺), and to envisage its potential influence on the homeostatic equilibria of essential metal ions. The chelating ability of P1 toward these ions, not higher than that of the corresponding deferiprone, contributes to render P1 a more selective iron chelator.

The reaction of the bis(1,2-dithiolene) complex [Pd(Me₂timdt)₂] (1; Me₂timdt^•– = monoreduced 1,3-dimethyl-2,4,5-trithioxoimidazolidine) with Br₂ yielded the complex [Pd(Me₂timdt)Br₂] (2), which was reacted with Na₂mnt (mnt^2– = 1,2-dicyano-1,2-ethylenedithiolate) to give the neutral mixed-ligand complex [Pd(Me₂timdt)(mnt)] (3). Complex 3 shows an intense solvatochromic near-infrared (NIR) absorption band falling between 955 nm in DMF and 1060 nm in CHCl₃ (ε = 10700 M^–1 cm^–1 in CHCl₃). DFT calculations were used to elucidate the electronic structure of complex 3 and to compare it with those of the corresponding homoleptic complexes 1 and [Pd(mnt)₂] (4). An in-depth comparison of calculated and experimental structural and vis–NIR spectroscopic properties, supported by IEF-PCM TD-DFT and NBO calculations, clearly points to a description of 3 as a dithione-dithiolato complex. For the first time, a broken-symmetry (BS) procedure for the evaluation of the singlet diradical character (DC) of heteroleptic bis(1,2-dithiolene) complexes has been developed and applied to complex 3. The DC, predominant for 1 (n_DC = 55.4%), provides a remarkable contribution to the electronic structures of the ground states of both 3 and 4, showing a diradicaloid nature (n_DC = 24.9% and 27.5%, respectively). The computational approach developed here clearly shows that a rational design of the DC of bis(1,2-ditiolene) metal complexes, and hence their linear and nonlinear optical properties, can be achieved by a proper choice of the 1,2-dithiolene ligands based on their electronic structure.