Chemical reduction of [Mo 2 Cp 2 (µ-Cl)(µ-PA 2 )-(CO) 2 ] (A ) Cy, Ph, OEt) gives the corresponding alkaline metal salts of the triply bonded anions [Mo 2 -Cp 2 (µ-PA 2 )(µ-CO) 2 ] -, which exhibit both molybdenum and oxygen nucleophilic sites. The PCy 2 anion reacts easily with NH 4 + , [AuCl(PR 3 )], or MeI to give unsaturated dicarbonyls [Mo 2 Cp 2 (µ-X)(µ-PA 2 )(CO) 2 ] (X ) H, AuPR 3 , Me), while [Me 3 O]BF 4 gives the methoxycarbyne [Mo 2 Cp 2 (µ-COMe)(µ-PCy 2 )(µ-CO)] and allyl chloride rearranges to give the unsaturated alkenyl complex [Mo 2 -Cp 2 (µ-PCy 2 )(µ-CMeCH 2 )(CO) 2 ].

Dinuclear N-heterocyclic dicarbene gold(I) complexes of general formula [Au(2)(RIm-Y-ImR)(2)](PF(6))(2) (R = Me, Cy; Y = (CH(2))(1-4), o-xylylene, m-xylylene) have been synthesized and screened for their luminescence properties. All the complexes are weakly emissive in solution whereas in the solid state some of them show significant luminescence intensities. In particular, crystals or powders of the complex with R = Me, Y = (CH(2))(3) exhibit an intense blue emission (λ(max) = 450 nm) with a high quantum yield (Φ(em) = 0.96). The X-ray crystal structure of this complex is characterized by a rather short intramolecular Au···Au distance (3.272 Ǻ). Time dependent density functional theory (TDDFT) calculations have been used to calculate the UV/vis properties of the ground state as well as of the first excited state of the complex, the latter featuring a significantly shorter Au···Au distance.

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Four novel dinuclear N-heterocyclic dicarbene gold(I) complexes with a propylene linker between the carbene moieties have been synthesized and their luminescence and electrochemical properties, together with their reactivity towards bromine oxidative addition, have been screened. All the complexes emit in the solid state in the blue-green spectral range (400-500 nm) with appreciable intensities (Φ(em) up to ≈10%). In cyclic voltammetry, the Au(I)/Au(0) peak splits at low temperature into two separate peaks relative to the couples Au(I)-Au(I)/Au(I)-Au(0) and Au(I)-Au(0)/Au(0)-Au(0), thus indicating the presence of an Au···Au interaction in the dinuclear complex. Oxidative addition of bromine affords as a major or unique product Au(II)-Au(II) complexes most likely as a consequence of the interaction between the two gold centres favoured by the propylene linker.

Tetrathia[7]helicene-based phosphanes thiaheliphos (2a), nPr-thiaheliphos (2b) and di-nPr-thiaheliphos (2c) have been prepared from the 2,13-dilithio derivatives of thiahelicenes 1a–c by reaction with an excess of Ph2PCl. Protection of the air-sensitive products as BH3 adducts, from which the phosphanes 2a–c are easily regenerated on heating with ethanol, is described. New rhodium(I) complexes 8 and 9 were obtained by reaction of 2c with [Rh(COD)2]+[BF4]– and [BARF]–, respectively, which were converted by oxidation into the chelating phosphane–phosphane oxide RhI complexes 10 and 11. The monophosphane 5 was similarly prepared, andreaction of the dilithio species with ClP(O)(OEt)2 gave the diphosphonate 17, which was characterized by X-ray crystallography. Comparison of data from DFT calculations (B3LYP/SVP) on 2c, 8 and 10 and X-ray data for 17 reveals a strong tension within the thiaheliphos ligands that is partially relaxed by increasing the Rh–P distances and the bite angle of the chelating ligand. Compound (P)-(+)-1c, obtained by chromatographic resolution, was transformed into optically pure (P)-(+)-2c, which was used in the asymmetric hydrogenation of itaconic acid ester and methyl 2-acetamidoacrylate (product ees up to 40%)