Carlo Manassero

Cooperation between Cis and Trans Influences in cis-PtII(PPh3)2 Complexes: Structural, Spectroscopic, and Computational Studies

The relevance of cis and trans influences of some anionic ligands X and Y in cis-[PtX(2)(PPh(3))(2)] and cis-[PtXY(PPh(3))(2)] complexes have been studied by the X-ray crystal structures of several derivatives (X(2) = (AcO)(2) (3), (NO(3))(2) (5), Br(2) (7), I(2) (11); and XY = Cl(AcO) (2), Cl(NO(3)) (4), and Cl(NO(2)) (13)), density functional theory (DFT) calculations, and one bond Pt-P coupling constants, (1)J(PtP). The latter have allowed an evaluation of the relative magnitude of both influences. It is concluded that such influences act in a cooperative way and that the cis influence is not irrelevant when rationalizing the (1)J(PtP) values, as well as the experimental Pt-P bond distances. On the contrary, in the optimized geometries, evaluated through B3LYP/def2-SVP calculations, the cis influence was not observed, except for compounds ClPh (21), Ph(2) (22), and, to a lesser extent, Cl(NO(2)) (13) and (NO(2))(2) (14). A natural bond order analysis on the optimized structures, however, has shown how the cis influence can be related to the s-character of the Pt hybrid orbital involved in the Pt-P bonds and the net atomic charge on Pt. We have also found that in the X-ray structures of cis-[PtX(2)(PPh(3))(2)] complexes the two Pt-X and the two Pt-P bond lengths are different each other and are related to the conformation of the phosphine groups, rather than to the crystal packing, since this feature is observed also in the optimized geometries.

Gold(III) six-membered N boolean AND C boolean AND N pincer complexes: synthesis, structure, reactivity and theoretical calculations

The first six-membered gold(III) N^C^N pincer complex was obtained in good yield, under very mild conditions, by transmetalation of [Hg(κC-N^C^N)Cl] (N^CH^N = 1,3-bis(pyridin-2-ylmethyl)benzene, HL(1)) with Na[AuCl(4)]. The X-ray crystal structure of [Au(N^C^N)Cl][PF(6)] showed that the fused six-membered metallacycles each exist in a strongly puckered boat conformation. As shown by the (1)H NMR spectra in various solvents, the same structure is also retained in solution: no inversion of the six-membered metallacycles is observed in DMSO up to 95 °C. This correlates well with a reaction barrier of 17.5 kcal/mole, as determined by quantum chemical calculations. The reactivity of the present pincer complex is compared to that of the analogous 1,3-bis(2-pyridyl)benzene, HL(2), derivative, which has five-membered fused metallacycles. Sharp differences are found in the reactions with phosphines, such as PPh(3) and dppe (1,2-bis-diphenylphosphino-ethane), and with silver salts. Theoretical calculations were carried out on the two pincer complexes in order to try to understand these differences, and we found that the gold-chlorine bond is significantly stronger in the case of the complex containing five-membered metallacyclic rings.

Structural variations, electrochemical properties and computational studies on monomeric and dimeric Fe-Cu carbide clusters, forming copper-based staple arrays.

The halide ligands of [Fe(4)C(CO)(12)(CuCl)(2)](2-) (1) and [Fe(5)C(CO)(14)CuCl](2-) (2) can be displaced by N-, P- or S-donors. Beside substitution, the clusters easily undergo structural rearrangements, with loss/gain of metal atoms, and formation of Fe(4)Cu/Fe(4)Cu(3) metallic frameworks. Thus, the reaction of 1 with excess dppe yielded [{Fe(4)C(CO)(12)Cu}(2)(μ-dppe)](2-) (3). [{Fe(4)C(CO)(12)Cu}(2)(μ-pyz)](2-) (4) was obtained by reaction of 2 with Ag(+) and pyrazine. [Fe(4)C(CO)(12)Cu-py](-) (5) was formed more directly from [Fe(4)C(CO)(12)](2-), [Cu(NCMe)(4)](+) and pyridine. [Fe(4)Cu(3)C(CO)(12)(μ-S(2)CNEt(2))(2)](-) (6) and [{Fe(4)Cu(3)C(CO)(12)(μ-pz)(2)}(2)](2-) (7) were prepared by substitution of the halides of 1 with diethyldithiocarbamate and pyrazolate, in the presence of Cu(i) ions. All of these products were characterized by X-ray analysis. 3 and 4 and 5 are square based pyramids, with iron in the apical sites, the bridging ligands connect the two copper atoms in 3 and 4. 6 and 7 are octahedral clusters with an additional copper ion held in place by the two bridging anionic ligands, forming a Cu(3) triangle with Cu-Cu distances ranging 2.63-3.13 Å. In 7, an additional unbridged cuprophilic interaction (2.75 Å) is formed between two such cluster units. DFT calculations were able to reproduce the structural deformations of 3-5, and related their differences to the back-donation from the ligand to Cu. Additionally, DFT found that, in solution, the tight ion pair [NEt(4)](2)7 is almost isoenergetic with the monomeric form. Thus, 3, 4 and 7 are entities of nanometric size, assembled either through conventional metal-ligand bonds or weaker electrostatic interactions. None of them allows electronic communication between the two monomeric units, as shown by electrochemistry and spectroelectrochemical studies. (dppe = PPh(2)CH(2)CH(2)PPh(2), pyz = pyrazine C(4)N(2)H(4), py = pyridine C(5)H(5)N, pz = pyrazolate C(3)N(2)H(3)(-)).

Telechelic Melt Polymer's Structure Variation Depending on Shear Deformation

We present the result of molecular dynamics (MD) simulations of bead and spring models of associating polymers at melt-like densities, both in static conditions and when a shear rate is applied. Specifically, we consider the response of telechelic polymers of general formula AB12A to four different values of shear rate. The A terminals tend to associate with each other and in bulk conditions form clusters or micelles. A reversible network or physical gel is formed by a large fraction of bridging chains that interconnect different clusters. The micelles assume different form depending on the interaction strengths. When a shear rate is applied, the clusters are broken and the chains tend to stretch.

Evaluation of viscosity and shear stress in a telechelic polymer when various shear rates are applied

We present the results of molecular dynamics (MD) simulations of bead and spring models of associating polymers at melt-like densities. We consider telechelic polymers of general formula AB12A at different values of shear rate. Under bulk conditions, A···A associations occur, leading to the construction of clusters or micelles that are interconnected by a number of bridging chains. This results in a physical gel or a reversible network, and the corresponding micelles assume different forms depending on the interaction strength. Whenever a low shear deformation is applied, the clusters are broken and there is a phase transition similar to that from a gel to a common non-Newtonian fluid. However, if the applied shear is increased, the chains stretch themselves (in a manner similar to nematic liquid crystal ordering) in a different way from what is seen without shear. In this work, we calculate the stress needed to yield a required deformation.