Structure and bonding of novel acyclic bisaminoarsenium cations.

The synthesis and characterization of a salt bearing a labile bisaminoarsenium cation of the type {[(Me3Si)2N]2As}(+) (9a) are described, which was obtained in the reaction of the chloroarsane [(Me3Si)2N]2AsCl (8) with GaCl3. Reacting 8 with AgOTf did not yield an arsenium salt, but the cyclo-diarsadiazane [(Me3Si)2NAs-µ-NSiMe3]2 (11) was obtained in excellent yields. Moreover, the reactivity of the analogous antimony species [(Me3Si)2N]2SbCl (12) was studied. In the reaction with GaCl3, the aminochlorostibenium salt [(Me3Si)2NSbCl](+)[(Me3Si)2N(GaCl3)2](-) (5) was isolated. In the reaction with AgOTf, substitution of the chlorine in 12 resulted in the formation of [(Me3Si)2N]2SbOTf (13), a compound with significant stibenium character. All new compounds have been fully characterized by means of X-ray, vibrational spectroscopy, CHN analysis, and NMR experiments. All compounds were further investigated by means of density functional theory and the bonding situation was accessed by natural bond orbital (NBO) analysis.

Reduction of dichloro(diaza-phospha)stibanes - isolation of a donor-stabilized distibenium dication.

A reaction of antimonytrichloride SbCl3 with potassium bis(terphenylimino)phosphide K[(TerN)2P] smoothly afforded a novel class of mixed diazadipnictanes, namely dichloro(diaza-phospha)stibane [Ter2N2P((III))Sb((III))Cl2], which is considered to exist as open chain-like and cyclic isomers in an equilibrium. [Ter2N2PSbCl2] is a versatile starting material for reduction and halide abstraction experiments. Halide abstraction led to the formation of a cyclic diazastibaphosphenium cation [P(µ-NTer)2SbCl](+). Upon reduction of [Ter2N2PSbCl2], the transient existence of the novel mixed biradicaloid [P(µ-NTer)2Sb] was proven by a trapping experiment with an alkyne, while reduction in the absence of trapping agents afforded the eight-membered heterocycle [Sb2-{µ-(TerN)2P}2]. This constitutional isomer of a dimerized biradicaloid features a bonding situation that indicates the presence of a donor-stabilized [Sb2](2+) ion.

Synthetic strategies to bicyclic tetraphosphanes using P1, P2 and P4 building blocks.

Different reactions of Mes* substituted phosphanes (Mes* = 2,4,6-tri-tert-butylphenyl) led to the formation of the bicyclic tetraphosphane Mes*P4Mes* (5) and its unknown Lewis acid adduct 5·GaCl3. In this context, the endo-exo isomer of 5 was fully characterized for the first time. The synthesis was achieved by reactions involving "self-assembly" of the P4 scaffold from P1 building blocks (i.e. primary phosphanes) or by reactions starting from P2 or P4 scaffolds (i.e. a diphosphene or cyclic tetraphosphane). Furthermore, interconversion between the exo-exo and endo-exo isomer were studied by (31)P NMR spectroscopy. All compounds were fully characterized by experimental as well as computational methods.

5-HT(1A)-receptor over-expressing mice: genotype and sex dependent responses to antidepressants in the forced swim-test.

Deficiencies in serotonergic neurotransmission are involved in the pathophysiology of depression. Due to its modulatory effect on serotonin (5-HT) release, the 5-HT(1A)-receptor is thought to play a decisive role in the therapy of this mood disorder. However, it is not fully understood how antidepressant effects are mediated by pre- and postsynaptic receptor sites. In this study we examined the impact of postsynaptic 5-HT(1A)-receptor over-expression in corticolimbic areas of male and female mice on the performance in the forced swim-test (FST). Furthermore, we investigated their response to the serotonin selective reuptake inhibitor (SSRI) citalopram in comparison to the selective noradrenaline reuptake inhibitor reboxetine, as well as the partial 5-HT(1A)-receptor agonists, buspirone and S 15535. Additionally, these drugs were evaluated in the open field-test in order to observe effects on motor activity. The density of 5-HT(1A)-receptors in discrete corticolimbic regions was determined in detail by quantitative autoradiography with [(3)H]8-OH-DPAT to investigate genotype as well as sex dependent differences in the expression pattern. [(3)H]8-OH-DPAT binding differed depending on sex with female mice of both genotypes displaying higher receptor binding in distinct brain areas. In the FST untreated male but not female over-expressing (OE) mice showed an antidepressant-like behaviour compared to wild-type (WT) mice. Citalopram yielded an antidepressant effect without influencing locomotor activity in OE mice but not in WT mice. Reboxetine had no antidepressant-like effect in OE mice, but sex-dependently in WT mice. The two partial agonists, buspirone and S 15535 produced no antidepressant-like activity in both genotypes and sexes, but aberrant motor effects. The antidepressant-like phenotype of male transgenic mice accounts for an involvement of postsynaptic 5-HT(1A)-receptors in the FST behaviour. In addition, the selective over-expression of postsynaptic 5-HT(1A)-receptors in mice contributes to the antidepressant response to citalopram in the FST. Although further pharmacological analysis is required, the data provide novel support for a role of postsynaptic 5-HT(1A)-receptors in the effects of SSRIs.