Synthesis and characterization of non-bridging mono- and bis-σ-η(1)-alkynyl derivatives of the phosphido-bridged hexaplatinum core [Pt6(µ-PBu(t)2)4(CO)4](2+).

Several mono- or bis-alkynyl derivatives of general formula Pt6(µ-PBu(t)2)4(CO)4X(C[triple bond, length as m-dash]C-R), Pt6(µ-PBu(t)2)4(CO)4(C[triple bond, length as m-dash]C-R)2 or Pt6(µ-PBu(t)2)4(CO)4(C[triple bond, length as m-dash]C-R)(C[triple bond, length as m-dash]C-R') were obtained under Sonogashira type conditions. The new clusters have been characterized with microanalysis and using IR and multinuclear NMR spectroscopy. The crystal and molecular structures of Pt6(µ-PBu(t)2)4(CO)4(C[triple bond, length as m-dash]C-R)2 (R = H, C6H4-4-n-C5H11) are presented and electrochemical and spectroelectrochemical studies of some representative compounds are also reported.

Chemistry and biology of two novel gold(I) carbene complexes as prospective anticancer agents.

Two novel gold carbene compounds, namely, chlorido (1-butyl-3-methyl-imidazole-2-ylidene) gold(I) (1) and bis(1-butyl-3-methyl-imidazole-2-ylidene) gold(I) (2), were prepared and characterized as prospective anticancer drug candidates. These compounds consist of a gold(I) center linearly coordinated either to one N-heterocyclic carbene (NHC) and one chloride ligand (1) or to two identical NHC ligands (2). Crystal structures were solved for both compounds, the resulting structural data being in good agreement with expectations. We wondered whether the presence of two tight carbene ligands in 2 might lead to biological properties distinct from those of the monocarbene complex 1. Notably, in spite of their appreciable structural differences, these two compounds manifested similarly potent cytotoxic actions in vitro when challenged against A2780 human ovarian carcinoma cells. In addition, both were able to overcome resistance to cisplatin in the A2780R line. Solution studies revealed that these gold carbene complexes are highly stable in aqueous buffers at physiological pH. Their reactivity with proteins was explored: no adduct formation was detected even upon a long incubation with the model proteins cytochrome c and lysozyme; in contrast, both compounds were able to metalate, to a large extent, the copper chaperone Atox-1, bearing a characteristic CXXC motif. The precise nature of the resulting gold-Atox-1 adducts was elucidated through ESI-MS analysis. On the basis of these findings, it is proposed that the investigated gold(I) carbene compounds are promising antiproliferative agents warranting a wider pharmacological evaluation. Most likely these gold compounds produce their potent biological effects through selective metalation and impairment of a few crucial cellular proteins.

Synthesis and electrochemical characterization of hexanuclear platinum bis-pseudohalides.

The hexanuclear phosphido-bridged dication [Pt6(µ-PBu(t)2)4(CO)6](2+), (1)(2+), reacts under mild conditions with pseudo-halide anions (CN(-), NCO(-), NCS(-)) to afford the corresponding neutral bis-substituted clusters Pt6(µ-PBu(t)2)4(CO)4X2 (2, X = CN; 3, X = SCN; 4, X = NCO). The reaction with sodium azide affords 4, which may arise from the formation of the intermediate bis-azido derivative Pt6(µ-PBu(t)2)4(CO)4(N3)2, 5, and CO. These react rapidly with each other affording 4 and N2. Cluster 5 was alternatively prepared as a stable compound by reacting with NaN3 the neutral cluster Pt6(µ-PBu(t)2)4(CO)4(OTf)2, 14, which contains two weakly bonded triflate anions. As expected, 5 reacts with carbon monoxide (1 atm) affording cluster 4 instantaneously and quantitatively. The new pseudo-halide clusters 2-5, which are interesting potential precursors of cluster-containing molecular frameworks, have been characterized by IR and multinuclear NMR spectroscopy. The solid state structures of clusters 2-4 have also been studied by single-crystal X-ray diffractometry. The main features of the molecular structures remain similar to those of many related congeners described previously; in addition, an interesting reversible phase transition was observed in the crystal structure of cluster 3. As their known congeners, the clusters undergo two reversible one-electron reductions and an irreversible oxidation. An excellent linear correlation was found between the redox potentials of the cathodic processes and Lever's ligand parameter E(L).

Unprecedented reversible coupling of alkynyl and phosphide ligands on a dinuclear platinum framework.

The reductive coupling of the bridging phosphide and the adjacent [sigma]-alkynyl moieties in [Pt2(mu-P(t)Bu2){mu,eta1:eta2-C(Ph)CH2}(C[triple bond]C-Ph)(CO)(P(t)Bu2H)(Br)] is promoted by bromide abstraction and is reversed by adding N(n)Bu4Br.

Trinuclear and hexanuclear platinum clusters as building blocks for organometallic one-dimensional structures.

The reaction between the new hexa- and trinuclear clusters [Pt6](CC-C6H4-CCH)2, (4) [[Pt6] = Pt6(CO)4(mu-PBu(t)2)4], and [Pt3]Cl, (6) [[Pt3] = Pt3(mu-PBu(t)2)3(CO)2], in CuI/Amine gives the thermally and air stable [Pt6](CC-C6H4-CC[Pt3])2 (7), where the cluster units are separated by conjugated 1,4-diethynylphenyl groups.