ß-Diversity partitioning of moth communities within and between different forest types.

The partitioning of ß-diversity is a recurrent practice in biogeographic and ecological studies that can provide key insights for land management, such as identification of biodiversity hot-spots. In this study, we used Baselga's metrics to measure the contribution of spatial turnover (ßsim) and nestedness-resultant dissimilarity (ßnes) to overall ß-diversity (ßsor) within- and between-forest types. We analyzed a presence/absence dataset concerning 593 species of nocturnal Lepidoptera sampled within chestnut, silver fir, beech, and black pine forests of southern Italy. Ordination methods and analysis of similarities were used to assess the relative contribution of ßsim and ßnes to ßsor, and to assess their relationships with variables linked to the experimental design and known to be determinant for insect diversity and abundance. We found that ßsor was mostly due to turnover, around 98.5% in ß-diversity assessment of the whole sample, and around 91% in ß-diversity assessment of individual forests. Using ordination analyses based on ßsim, stands were grouped according to forest type, while ßnes alone was used to ordinate stands coherently with their species richness. Nevertheless, the addition of ßnes to ßsim produced a more ecologically coherent grouping of stands within individual forest types, and ßnes alone was able to recognize patterns determined by human disturbance. In conclusion, we demonstrate that ß-diversity partitioning can help to detect differences in magnitude and role of processes determining the composition of forest moth communities as in different forests the same pattern can be due to opposite processes, providing strong ecological insights into managing forest biodiversity.

Intriguing I2 Reduction in the Iodide for Chloride Ligand Substitution at a Ru(II) Complex: Role of Mixed Trihalides in the Redox Mechanism.

The compound [Ru(CN(t)Bu)4(Cl)2], 1, reacts with I2, yielding the halogen-bonded (XB) 1D species {[Ru(CN(t)Bu)4(I)2]·I2}n, (2·I2)n, whose building block contains I(-) ligands in place of Cl(-) ligands, even though no suitable redox agent is present in solution. Some isolated solid-state intermediates, such as {[Ru(CN(t)Bu)4(Cl)2]·2I2}n, (1·2I2)n, and {[Ru(CN(t)Bu)4(Cl)(I)]·3I2}n, (3·3I2)n, indicate the stepwise substitution of the two trans-halide ligands in 1, showing that end-on-coordinated trihalides play a key role in the process. In particular, the formation of ClI2(-) triggers electron transfer, possibly followed by an inverted coordination of the triatomic species through the external iodine atom. This allows I-Cl separation, as corroborated by Raman spectra. The process through XB intermediates corresponds to reduction of one iodine atom combined with the oxidation of one coordinated chloride ligand to give the corresponding zerovalent atom of I-Cl. This redox process, explored by density functional theory calculations (B97D/6-31+G(d,p)/SDD (for I and Ru atoms)), is apparently counterintuitive with respect to the known behavior of the corresponding free halogen systems, which favor iodide oxidation by Cl2. On the other hand, similar energy barriers are found for the metal-assisted process and require a supply of energy to be passed. In this respect, the control of the temperature is fundamental in combination with the favorable crystallizations of the various solid-state products. As an important conclusion, trihalogens, as XB adducts, are not static in nature but are able to undergo dynamic inner electron transfers consistently with implicit redox chemistry.

Electron-rich bonding and the importance of s,p mixing as one moves across a period: a lesson from the LiSn system.

The electronic structure of an unusual LiSn phase (computed using band structure calculations in the framework of the extended Hückel tight binding theory) is the starting point for a general analysis of the variation of electron-rich multicenter bonding across a period. The LiSn crystal structure of Müller and Schäfer in question contains 2D slabs of Sn atoms arranged as microscopic stairs and intercalated by Li atoms. Discrepancies between an electron count derived from a recent extension of the Zintl-Klemm rules to electron-rich systems (5(2/3) electrons) and the experimental one (5 electrons for the Sn sublattice) and other failures of chemical "common sense" emerge in the analysis. The key for interpretation of a series of puzzling results was found in the comparative analysis of the Sn net with other main group element hypervalent slabs. Increasing s,p-mixing as one moves from the right to the left side of the same row of the periodic table is responsible for these effects. The result is that a lower electron count is found in the Sn slabs relative to the one expected from the extended Zintl-Klemm theory. The effect should also occur in discrete molecules. We also showed that the Li atoms have a role in the determination of the final structure, not only because of their small size but also through the degree of the electron transfer to the Sn sublattice.

Synthesis and structure of the cluster ion pair [Ru3(CO)9[mu-P(NPri2)2]3][Ru6(CO)15(mu 6-C)[mu-P(NPri2)2]]. A theoretical overview of M3(mu-PR2)3 frameworks.

The compound [Ru3(CO)9[mu-P(NPri2)2]3][Ru6(CO)15(mu 6-C)[mu-P(NPri2)2]] (1), obtained via the addition of PCl(NPri2)2 to K2[Ru4(CO)13], crystallizes in the monoclinic space group P2l/c with a = 15.537(8) A, b = 36.151(16) A, c = 19.407(5) A, beta = 91.14(2) degrees, Z = 4, and R = 0.069 for 8006 observed reflections. The unit cell is unusual in that it contains both a typical octahedral Ru6 cluster anion (1a), featuring an encapsulated carbide, and a symmetrical phosphido bridge, in addition to a 50-electron trinuclear cluster cation [Ru3(CO)9[mu-P(NPri2)2]3]+ (1c). The latter, with approximate D3h symmetry, exhibits long Ru-Ru distances (> or = 3.15 A). Among the family of clusters with M3(mu-PR2)3 cores and different numbers of both electrons (TEC) and terminal ligands (LxLyLz), 1c is unique in that it is a 333 stereotype with 50 valence electrons. MO calculations permit us to predict the existence of redox congeners of 1c clusters and related 48e Re3 clusters. This work also presents a summary of the relationships between the electronic and the geometric structures for all known M3LxLyLz(mu-PR2)3 species. The basic stereochemical features are influenced by the total-electron count and, hence, by the degree of M-M bonding, as well as the remarkable flexibility of the phosphido bridging ligands. The mu-PR2 ligands need not necessarily lie in the M3 plane, and a wide range of M-P-M angles (as small as 72 degrees or as large as 133 degrees) have been observed.