Building C(sp3) Molecular Complexity on 2,2′-Bipyridine and 1,10-Phenanthroline in Rhenium Tricarbonyl Complexes

The reactions of [Re(N-N)(CO)₃(PMe₃)]OTf (N-N=2,2′-bipyridine, bipy; 1,10-phenanthroline, phen) compounds with tBuLi and with LiHBEt₃ have been explored. Addition to the N-N chelate took place with different site-selectivity depending on both chelate and nucleophile. Thus, with tBuLi, an unprecedented addition to C5 of bipy, a regiochemistry not accessible for free bipy, was obtained, whereas coordinated phen underwent tBuLi addition to C2 and C4. Remarkably, when LiHBEt₃ reacted with [Re(bipy)(CO)₃(PMe₃)]OTf, hydride addition to the 4 and 6 positions of bipy triggered an intermolecular cyclodimerization of two dearomatized pyridyl rings. In contrast, hydride addition to the phen analog resulted in partial reduction of one pyridine ring. The resulting neutral Re^I products showed a varied reactivity with HOTf and with MeOTf to yield cationic complexes. These strategies rendered access to Re^I complexes containing bipy- and phen-derived chelates with several C(sp³) centers.     

Franck-Condon Factors and R-Centroids for the B-X Transition of La18O and La16O,Including Rotation-Vibration Interaction

FRANCK-CONDON FACTORS AND R-CENTROIDS FOR THE GREEN-YELLOW SYSTEM OF LA¹⁶O AND LA¹⁸O ARE REPORTED. CALCULATION INCLUDES ROTATION-VIBRATION INTERACTION, AND A SIGNIFICANT VARIATION WHEN THE ROTATIONAL QUANTUM NUMBER CHANGES HAS BEEN FOUND.     

Essential collections for equilibrium concepts

The aim of this study is to identify and characterize the parts of an extensive form game that are ??relevant?? to determining whether the outcome of a certain strategy profile is an equilibrium outcome. We formally define what we mean by ??relevant?? and refer to the associated collection of information sets as essential. We apply this idea to a number of classic equilibrium concepts and discuss some implications of our approach.     

Radical anions containing the dioxidated 1,2,5‐thiadiazole heterocycle. Part II

Radical anions from several 3,4‐aryl‐disubstituted derivatives of 1,2,5‐thiadiazole 1,1‐dioxide were accumulated through chemical reduction of the substrates in aprotic solvents. The radical anions were characterized by electron spin resonance and cyclic voltammetry. DFT theoretical calculations were also performed for the 3,4‐diphenyl derivative. The course of the reductions was followed using cyclic voltammetry. Uncommon reductants, such as amides, were found to be effective under certain conditions. Copyright © 2010 John Wiley & Sons, Ltd.