Primary amino-functionalized N-heterocyclic carbene ligands as support for Au(I)···Au(I) interactions: structural, electrochemical, spectroscopic and computational studies of the dinuclear [Au2(NH2(CH2)2imMe)2][NO3]2.

The N-heterocyclic carbene (NHC) precursor, 1-(2-aminoethyl)-3-methylimidazolium nitrate, [NH(2)(CH(2))(2)imMe)]NO(3) ([3][NO(3)]) reacted with Ag(2)CO(3) in dimethyl sulfoxide readily yielding a Ag(I)-(NHC-NH(2)) complex presenting limited stability in solution. The in situ carbene transfer reaction of the latter with [Au(tht)Cl] afforded the first example of a dinuclear gold(I) complex [Au(2)(NH(2)(CH(2))(2)imMe)(2)][NO(3)](2) ([5][NO(3)](2)) bearing a primary amino-functionalized NHC ligand. The complex has been characterized by NMR, mass spectrometry, X-ray crystallography and cyclic voltammetry; the electrochemical behaviour and photophysical properties of [5][NO(3)](2) have been also investigated and the experimental data have been compared with density functional theory (DFT) and Time Dependent (TDDFT) calculations.

[3+2+1] cycloaddition involving alkynes, CO and bridging vinyliminium ligands in diiron complexes: a dinuclear version of the Dötz reaction?

The vinyliminium complex [Fe2{mu-eta(1):eta(3)-C(SiMe3)=CHC=N(Me)2}(mu-CO)(CO)(Cp)2][SO3CF3] reacts with HC[triple bond]CR (R = CPh2OH), affording a mixture of the 2,4,6-trisubstituted oxo-eta(5)-cyclohexadienyl complex [Fe{eta(5)-C6H2O(NMe2)(SiMe3)(R)}(Cp)], the 2,6-disubstituted phenol C6H3R(NMe2)OH (R = CHPh2) and 1,2,4-trisubstituted ferrocene [1-NMe2-2-R-4-SiMe3-Fc]. The corresponding reaction with HC[triple bond]CR (R = CMe2OH) yields analogous products: [Fe{eta(5)-C6H2O(NMe2)(SiMe3)(R')}(Cp)] (R' = CMe=CH2), the phenol C6H3R'(NMe2)OH together with [1-NMe2-2-R-4-SiMe3-Fc].

Synthesis of new poly(propylenimine) dendrimers DAB-dendr-[NH(O)COCH2CH2OC(O)C5H4Rh(NBD)](n) [n=4, 8, 16, 32, 64] functionalized with alkoxycarbonylcyclopentadienyl complexes of rhodium(I).

The reaction between [Rh[C5H4CO2(CH)2OH](NBD)] (1) and 1,1'-carbonyldiimidazole (CDI) leads to the new CO2-imidazole functionalized alkoxycarbonylcyclopentadienyl complex [Rh[C5H4CO2(CH2)2O2C-Im](NBD)] (2) (Im=imidazole). The latter was treated with five generations of poly(propylenimine) dendrimers DAB-dendr-(NH2)(n) [n=4, 8, 16, 32, 64] (DAB=diaminobutane) to accomplish the synthesis of the new organometallic dendritic macromolecules DAB-dendr-[NH(O)COCH2CH2OC(O)C5H4Rh(NBD)](n) [n=4 (4), 8 (5), 16 (6), 32 (7), 64 (8)] based on flexible poly(propylenimine) dendrimer cores, built up to the fifth generation. Spectroscopic characterization of all the new compounds will be presented and discussed.