Experimental and computational investigation on the formation pathway of [RuCl2(CO)2(ERR')2] (E = S, Se, Te; R, R' = Me, Ph) from [RuCl2(CO)3]2 and ERR'.

The pathways to the formation of the series of [RuCl2(CO)2(ERR')2] (E = S, Se, Te; R, R' = Me, Ph) complexes from [RuCl2(CO)3]2 and ERR' have been explored experimentally in THF and CH2Cl2, and computationally by PBE0-D3/def2-TZVP calculations. The end-products and some reaction intermediates have been isolated and identified by NMR spectroscopy, and their crystal structures have been determined by X-ray diffraction. The relative stabilities of the [RuCl2(CO)2(ERR')2] isomers follow the order cct > ccc > tcc > ttt ≈ ctc (the terms c/t refer to cis/trans arrangement of the ligands in the order of Cl, CO, and ERR'). The yields were rather similar in both solvents, but the reactions were significantly faster in THF than in CH2Cl2. The highest yields were observed for the telluroether complexes, and the yields decreased with lighter chalcogenoethers. PBE0-D3/def2-TZVP calculations indicated that the reaction path is independent of the nature of the solvent. The substitution of one CO ligand of the intermediate [RuCl2(CO)3(ERR')] by the second ERR' shows the highest activation barrier and is the rate-determining step in all reactions. The observed faster reaction rate in THF than in CH2Cl2 upon reflux can therefore be explained by the higher boiling point of THF. At room temperature the reactions in both solvents proceed equally slowly. When the reaction is carried out in THF, the formation of [RuCl2(CO)3(THF)] is also observed, and the reaction may proceed with the substitution of THF by ERR'. The formation of the THF complex, however, is not necessary for the dissociation of the [RuCl2(CO)3]2. Thermal energy at room temperature is sufficient to cleave one of the bridging Ru-Cl bonds. The intermediate thus formed undergoes a facile reaction with ERR'. This mechanism is viable also in non-coordinating CH2Cl2.

An evaluation of the use of olanzapine pamoate depot injection in seriously violent men with schizophrenia in a UK high-security hospital.

BACKGROUND: Oral olanzapine is a well-established treatment for patients suffering from schizophrenia. Advantages of depot olanzapine may include improved compliance. However, it is expensive, causes metabolic side effects, and carries a risk of postinjection syndrome. Clinical trials have shown olanzapine pamoate to be effective, but further work is needed in this area. This study was a retrospective service evaluation, carried out in a high-security hospital, where the majority of patients have complex, treatment resistant schizophrenia spectrum disorder and a very high propensity for violence. Compliance is a significant problem, both in the high-security setting and on discharge. There has been no previous published work that the authors are aware of evaluating the effects of olanzapine pamoate in this subgroup of patients. METHODS: The aim of the study was to evaluate the clinical efficacy of olanzapine pamoate, its effect on violence as well as its side effects, in a high-security setting for the first time. Anonymized patient records were used to identify the main outcome measure and clinical global improvement, and to ascertain secondary outcome measures which included seclusion hours, risk of violence and side effects. Metabolic parameters and number of incidents were also recorded. Eight patients were treated with olanzapine pamoate. RESULTS: Six showed an improvement in symptoms, with an associated decrease in violence and number of incidents. Four showed an associated decrease in seclusion hours. Two showed an increase in body mass index and two showed an increase in glucose. CONCLUSIONS: The findings of this study are important in showing that all patients who responded to olanzapine pamoate also showed a decrease in violent behaviour. The potential anti-aggression effects of olanzapine pamoate may represent a very promising area for further work. A depot antipsychotic medication that reduces violence could have significant implications for management of high-security patients.

Preparation, structure, and metallophilic interactions of dinuclear silver(I) and copper(I) complexes of selenium diimides.

The complexes [M(2){mu-N,N'-Se(NR)(2)}(2)](CF(3)SO(3))(2) (1, M = Ag, R = (t)Bu; 2, M = Ag, R = Ad; 3, M = Cu, R = (t)Bu; 4, M = Cu, R = Ad; Ad = 1-adamantyl) were prepared in good yields from the reaction of the corresponding selenium diimide with silver or copper triflate in toluene and were characterized in solution using multinuclear NMR spectroscopy. Recrystallization of 1-4 from a variety of solvents produced 1.2CH(2)Cl(2), 2(AdNH(3))(CF(3)SO(3)) (a few crystals), 3.2thf, and 4.1/2C(7)H(8), which were characterized by X-ray crystallography. All of these salts contain a metallacyclic [M(2){mu-N,N'-Se(NR)(2)}(2)](2+) [M = Ag, Cu; R = (t)Bu, Ad] cation, the frameworks of which exhibit M...M close contacts of 2.7384(9), 2.751(2), 2.556(2)-2.569(2), and 2.531(1) A, respectively. The M...M interaction was further explored by PBE/def-TZVP calculations of the dications [M(2){mu-N,N'-Se(NR)(2)}(2)](2+) (M = Ag, Cu; R = H, Me, (t)Bu, Ad). The geometry optimizations yielded metric parameters that were in good agreement with experimental values, where available. For both metals, it was observed that the M...M distance became shorter, as the organic substituent on nitrogen became bulkier. At the same time, the metallacyclic framework deviated more significantly from planarity. A survey of related dinuclear silver(I) and copper(I) complexes showed that, while there is some correlation between the bite size and the M...M distance, the latter is more dependent on the deviation from planarity of the D(2)M...MD(2) fragment. Atoms in molecules calculations clearly showed the presence of a bond critical point between the two silver or copper centers, as well as two ring critical points. Our computational results are consistent with other recent molecular orbital studies at different levels of theory and indicate the existence of d(10)-d(10) closed-shell metallophilic interactions in 1-4.

Pyrolysis and UV photoelectron spectroscopy of bicyclo[3.2.0]hept-6-en-2-one; preparation and detection of cyclohepta-2(Z),4(E)-dien-1-one.

Flash vacuum pyrolysis of bicyclo[3.2.0]hept-6-en-2-one (1) in the source chamber of a UV photoelectron (PE) spectrometer using a CW CO2 laser as a directed heat source facilitated an electrocyclic ring expansion to yield the transient species cyclohepta-2(Z),4(E)-dien-1-one (2), the PE spectrum of which was compared to that of an authentic sample of cyclohepta-2(Z),4(Z)-dien-1-one (4) and confirmed a conrotatory ring opening of 1 that obeys the Woodward-Hoffmann rules.