Striking gold: A series of variously functionalized propynyl arenes was smoothly converted into indan‐2‐ones by a new gold(I)‐catalyzed oxidative cyclization process. [LAu]NTf2 (Tf=trifluoromethanesulfonyl) is a superior catalyst both in terms of yield and kinetics for the present transformation.

The reactivity of a set of prototypical (η6-arene)tricarbonylchromium complexes bearing amino, oxazolyl, and pyridyl ancillary ligands versus [Cp*RhCl2]2 and [Cp*IrCl2]2 has been investigated. Successful cyclometalation reactions were achieved essentially in the presence of hydrated sodium acetate with planar-prochiral 2-phenylpyridine and 3-methyl-2-phenylpyridine complexes with yields ranging from 60% to 92%. The most salient feature of the reported reactions is their stereoselectivity, as the only diastereomers to be produced are those with the Rh- and Ir-bound chloro ligand located trans with respect to the Cr(CO)3. According to X-ray diffraction analyses, a relative rac-(pR,T-4-S) configuration may be assigned to the complexes:  the Cp* ligand sits unexpectedly syn with respect to the tricarbonylmetal moiety. Introduction of the Cr(CO)3 moiety by treatment of cycloiridated 2-phenylpyridine with tricarbonyl(η6-naphthalene)chromium resulted in a unique diastereomer of the same relative configuration. Quantum calculations using the density functional theory were carried out on models of syn and trans-chloro isomers. Owing to strong electrostatic repulsion between the chloro ligand and the Cr(CO)3 moiety, the syn-chloro isomers were found less stable by 7−8 kcal/mol than the trans counterparts, suggesting that cyclorhodation and cycloiridation reactions are thermodynamically controlled.

White phosphorus, P4, was reacted in a stoichiometric manner with Ni(0) complexes or particles to produce nanoparticles of nickel phosphide.

In the last decadeo rganic-inorganic hybrid materials have becomeessential in materials science as they combine properties of both buildingb locks. Nowadays the main routes for their synthesis involve electrostatic coupling, covalent grafting, and/or solvente ffects. In this field, polyoxometalates (POMs) have emerged as interesting inorganic functional buildingb locks due to their outstanding properties. In the present work the well-known a-Keggin polyoxometalate, a-PW 12 O 40 3À (PW), is shown to form hybrid crystalline materials with industrial (neutral) polyethylene glycol oligomers (PEG) under mild conditions, that is, in aqueous medium and at room temperature. The formation of these materials originates from the spontaneous self-assembly of PW with EO x ,( EO = ethylene oxide)w ith at least four EO units (x > 4). The PW-PEG nanoassemblies, made of aP OM surrounded by about two PEG oligomers, are stabilized by electrostatic repulsions betweent he negatively charged PW anions.A ddition of NaCl, aimed at screening the inter-nanoassembly repulsions,i nduces aggregation and formationo f hybrid crystalline materials. Single-crystal analysiss howed ah igh selectivity of PW towards EO 5 -EO 6 oligomers from PEG200, which is made of am ixture of EO 3-8 .T herefore, ag eneral "soft" route to produce POM-organic composites is proposed here through the controlo fe lectrostatic repulsions between spontaneously formed nanoassemblies in water.H owever, this rational design of new POM hybrid (crystalline) materials with hydrophilic blocks, using such as imple mixing procedureo ft he components, requires ad eep understanding of the molecular interactions.

XRD, EXAFS and HR-TEM study reveals a strong correlation between AnO2 (An = Th and Pu) nanoparticle size and An(iv) local structure.

The widely used preparation of Ni(0) nanoparticles from [Ni(acac)(2)] (acac=acetylacetonate) and oleylamine, often considered to be a thermolysis or a radical reaction, was analyzed anew by using a combination of DFT modeling and designed mechanistic experiments. Firstly, the reaction was followed up by using TGA to evaluate the energy barrier of the limiting step. Secondly, all the byproducts were identified using NMR spectroscopy, mass spectrometry, FTIR, and X-ray crystallography. These methods allowed us to depict both main and side-reaction pathways. Lastly, DFT modeling was utilized to assess the validity of this new scheme by identifying the limiting steps and evaluating the corresponding energy barriers. The oleylamine was shown to reduce the [Ni(acac)(2)] complex not through a one-electron radical mechanism, as often stated, but as an hydride donor through a two-electron chemical reduction route. This finding has strong consequences not only for the design of further nanoparticles syntheses that use long-chain amine as a reactant, but also for advanced understanding of catalytic reactions for which these nanoparticles can be employed.

The monodeprotonation of [CH2(PPh2→BH3)­(PPh2E)] (E = S (6), O (7)) afforded [CH­(PPh2→BH3)­(PPh2E)]− (E = S (6 ‑ ), O (7 – )), whose structures were confirmed by X-ray crystallography. The kinetics of the second deprotonation appeared to be crucial in efficient synthesis of the corresponding dianions. Thus, the double deprotonation of 6 only led to 6 2– ; the analogous reaction with 7 was slower and resulted only in the partial formation of 7 2– . Double deprotonation of the compound [CH2(SiMe3)­(PPh2S)] (8) also resulted in the partial formation of [C­(SiMe3)­(PPh2S)]2‑ (8 2– ), whose structure was confirmed by X-ray crystallography. The rare monomeric Mg carbene compound [MgC­(PPh2→BH3)­(PPh2S)] (9) was obtained by the reaction of 6 with Mg­(nBu)2. The X-ray structure of 9 is presented.

The reactions of the samarium(II) complexes Tmp 2 Sm (Tmp = 2,3,4,5-tetramethyl-1H-phosphol-1-yl) and Cp* 2 Sm(THF) 2 (Cp* = 1,2,3,4,5-tetramethyl-2,4-cyclopentadien-1-yl) with pyridine were found to be different, despite the fact that the Cp* and Tmp π-ligands are similar in size. With Tmp 2 Sm, a simple adduct, Tmp 2 Sm(pyridine) 2 is isolated, while with Cp* 2 Sm(THF) 2 pyridine is dimerized with concomitant oxidation of samarium to form [Cp* 2 Sm-(C 5 H 5 N)] 2 [μ-(NC 5 H 5 −C 5 H 5 N)]. However, reaction of Tmp 2 Sm with acridine, a better π-acceptor than pyridine, did result in acridine dimerization and the isolation of [Tmp 2 Sm] 2 [μ-(NC 13 H 9 −C 13 H 9 N)]. DFT calculations on the model structures of Tmp 2 Sm and Cp* 2 Sm, and on the single electron transfer step from Sm to pyridine and acridine in these ligand environments, confirmed that, even though the Sm−πligand bonds are mostly ionic, the different electronic properties of the Tmp ligand versus that of Cp are responsible for the difference in reactivity of Tmp 2 Sm and Cp* 2 Sm.■ EXPERIMENTAL SECTION Computational Details. Calculations were performed with the GAUSSIAN 03 suite of programs. 10 DFT was applied by means of the