The indenyl complex [RuCl(η 5 -C 9 H 7 )(PPh 3 ) 2 ] (1) reacts with monodentate (L: PMePh 2 , PMe 2 Ph, PMe 3 ) or bidentate [L-L: Ph 2 PCH 2 PPh 2 (dppm), Ph 2 P(CH 2 ) 2 PPh 2 (dppe)] phosphines to give monosubstituted [RuCl(η 5 -C 9 H 7 )(PPh 3 )(L)], bisubstituted [RuCl(η 5 -C 9 H 7 )(L) 2 ], or chelated complexes [RuCl(η 5 -C 9 H 7 )(L-L)] in toluene or tetrahydrofuran. The corresponding cyclopentadienyl complex [RuCl(η 5 -C 5 H 5 )(PPh 3 ) 2 ] (2) reacts similarly, at higher temperatures or longer reaction times. In refluxing toluene, PMe 3 and dppm give ionic products [Ru(η 5 -C 9 H 7 )(L) 3 ]Cl. The kinetics of PPh 3 substitution by PMePh 2 and PMe 2 Ph in tetrahydrofuran yield first-order rate constants that are independent of the concentration or the nature of phosphine. Rate decrease in the presence of added PPh 3 or saturation behavior at high [PPh 3 ] indicates that the reaction proceeds by a dissociative mechanism, in which extrusion of PPh 3 is rate determining. Kinetics for the reaction with PMePh 2 in the temperature range 12-40 °C for the indenyl and 20-50 °C for the cyclopentadienyl complex give the following activation parameters: ∆H q) 26 ( 1 kcal mol -1 and ∆S q ) 11 ( 2 cal mol -1 K -1 for 1 and ∆H q) 29 ( 1 kcal mol -1 and ∆S q ) 17 ( 2 cal mol -1 K -1 for 2. Complex 1 is 1 order of magnitude more reactive than 2, indicating more efficient stabilization of 16-electron intermediates RuCl(η 5 -ligand)(PPh 3 ) by the indenyl group. Cyclic voltammetry measurements for [RuCl(η 5 -ligand)(L) 2 ] in dichloromethane indicate that indenyl or pentamethylcyclopentadienyl complexes are oxidized at lower potentials than cyclopentadienyl complexes. Kinetics and electrochemistry suggest that indenyl is electron donating toward the metal fragment, with respect to cyclopentadienyl.

Ein HRTEM‐Bild genügt, um eine Potentialabbildung als Startpunkt für eine Computersimulation zur Lösung komplexer Zeolithstrukturen aufzustellen. Die Atome werden zunächst randomisiert platziert und dann in Bereiche mit hohem Potential „gestoßen“ (siehe Schema). Modelle, die eine sinnvolle Bindungsgeometrie und gute Übereinstimmung mit dem HRTEM‐Bild aufweisen, werden als Kandidaten für die abschließende Strukturlösung ausgewählt.

Gold nanoparticles stabilized by two novel bifunctional fluorenyl thiols, generated in situ from 9,9-idodecyl-2,7-bis(acetylthio) fluorene (1) and 9,9-didodecyl-2,7-bis(acetylthiophenylethynyl) fluorene (2), exhibit bridged structures which self-assemble in parallel lines. The size, shape and structure of the AuNPs have been determined by means of dynamic light scattering (DLS), scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). AuNPs modified with fluorenyl thiol derivatives show diameters in the range of 3-7 nm. The linkage between the nanoparticles can be envisaged with the formation of dyads supported by TEM analysis and XPS measurements. Remarkably, investigation by scanning electron microscopy of the AuNP films revealed an ordered distribution of well-separated individual nanoparticles to form a 2D network. The formation of interconnected networks between AuNPs with different distances, depending on the nature of the thiol linkers (1) or (2), and the photoluminescence properties open perspectives for applications in optical devices and electronics

Intramolecular [2 + 2] cycloaddition of two C=C bonds in vinylidene complexes [Ru(eta5-C9H7){=C=C(R)H}(PPh3){kappa1-(P)-PPh2(C3H5)][BF4] affords cyclobutylidene complexes [Ru(eta5-C9H7){kappa2-(P,C)-(=CC(R)HCH2CHCH2PPh2)}(PPh3)][BF4], which can be also obtained by reaction of terminal alkynes with [Ru(eta5-C9H7)(PPh3){kappa3-(P,C,C)-PPh2(C3H5)}][PF6]. The reaction proceeds under mild conditions via vinylidene complexes, and the activation parameters were determined by kinetic studies.