Thermolysis of the single source precursor (Et2Bi)2Te in DIPB at 80 °C yielded phase-pure Bi4Te3 nanoparticles, while mixtures of Bi4Te3 and elemental Bi were formed at higher temperatures. In contrast, cubic Bi2Te particles were obtained by thermal decomposition of Et2BiTeEt in DIPB. Moreover, a dual source approach (hot injection method) using the reaction of Te(SiEt3)2 and Bi(NMe2)3 was applied for the synthesis of different pure Bi-Te phases including Bi2Te, Bi4Te3 and Bi2Te3, which were characterized by PXRD, REM, TEM and EDX. The influence of reaction temperature, precursor molar ratio and thermolysis conditions on the resulting material phase was verified. Moreover, reactions of alternate bismuth precursors such as Bi(NEt2)3, Bi(NMeEt)3 and BiCl3 with Te(SiEt3)2 were investigated.

The solid state structures of Et4Sb2 1 and Et4Bi2 2 were determined by single crystal Xray diffraction. Single crystals of 1 and 2 were grown in a closed quartz glass capillary under an inert argon atmosphere on the diffractometer using a specific IR-laser-assisted technique. 1 shows short intermolecular Sb•••Sb interactions, whereas the closest Bi•••Bi distances are longer than the sum of the van-der-Waals radii.

Structurally diverse carbocycles with two vicinal nitrogen-substituents were prepared in expedient three-component reactions from simple amines, aldehydes, and nitroalkenes. trans,trans-6-Nitrocyclohex-2-enyl amines were obtained in a one-pot domino reaction involving condensation, tautomerisation, conjugate addition, and nitro-Mannich cyclisation. Upon employment of less nucleophilic carboxamides, a concerted Diels-Alder cycloaddition mechanism operated to give the corresponding cis,trans-nitrocyclohexenyl amides. Both types of substituted carbocycles offer ample opportunities for chemical manipulations at the core and periphery. Ring oxidation with MnO2 affords substituted nitroarenes. Reduction with Zn/HCl provides access to various trans- and cis-diaminocyclohexenes, respectively, in a straight-forward manner. With enantiopure secondary amines, a two-step synthesis of chiral nitrocyclohexadienes was developed (82-94% ee).

A critical factor for the increased nucleophilicity of the pyridine nitrogen in 4-(dimethylamino)pyridine (DMAP) is electron donation via resonance from the amino group into the aromatic ring that increases electron density on the pyridine nitrogen. To explore how important this resonance effect is, 4-(dimethylaminomethyl)pyridine (DMAMP) was synthesized and the alkylation products of DMAP and DMAMP were compared. The methylene group between the pyridine ring and the amino group in DMAMP removes the possibility of resonance effects between the two nitrogen atoms. Alkylation of DMAP occurs exclusively at the pyridine nitrogen, whereas alkylation of DMAMP occurs exclusively at the amino group indicating that resonance effects are quite important. When these alkylations are carried out with a 1:1 equimolar ratio of CH3I and CH3CH2I, only methylated products are formed. This laboratory experiment is designed to teach students how to analyze the fundamental concepts of nucleophilicity and electrophilicity as a method of accurately predicting the reactivity of organic compounds. Molecular orbital calculations are used to examine the electron density present on each nitrogen atom of DMAP and DMAMP (as a measure of nucleophilicity) and to determine the stability of the possible products.