Genesis of Polynitrogen Compounds employing Silicon Substituted Cyclo[18]Carbon: A DFT Investigation.

Activation of molecular N2 and its catalytic ability to form NH3 using C17Si has been already reported. This current study reports the formation of exclusive polynitrogen clusters (N4 and N5) on the C17Si ring. The clusters are generated using N2 and N3 respectively. Physical and chemical property analyses of the clusters show that the N5 cluster exhibits greater stability than N4. The former is seen to experience reduced molecular strain compared to the latter owing to its co-planar geometry. The thermodynamic calculations of the systems further show that the formation of the N5 cluster is spontaneous compared to N4 on the C17Si ring.

Mechanistic Inquisition on the Reduction of C17Si(NH2)2 to NH3: A DFT Study.

Activation of molecular nitrogen by silicon-substituted cyclo[18]carbon and its ability to produce the C17Si-(NH2)2 derivative, as the precursor of NH3, has been recently reported. This specific acquisition has piqued an interest to investigate the possibility of NH3 formation with further addition of H2 molecules in the gaseous reaction media. The current investigations reported in this article show that two moles of molecular H2 generate two molecules of NH3 and a C17Si-H2 byproduct from its precursor. The catalyst gets restored by an in situ reaction between some unreacted C17Si-N2 and the byproduct in the media. This reaction also produces the next C17Si-(NH)2 adduct, which restarts the catalytic cycle for NH3 production again.

Activation and Conversion of Molecular Nitrogen to the Precursor of Ammonia on Silicon Substituted Cyclo[18]Carbon: a DFT Design.

Recent synthesis of sp-hybridized cyclo[18]carbon allotrope has attracted immense curiosity. Since then, a generous amount of theoretical studies concerning aromaticity, adsorption, and spectra of the molecule have been performed. However, very few stuides have been carried out concerning its reactivities and catalytic behaviour. In this article, a DFT-based inquisition has been reported regarding the reactivity of Si substituted cyclo[18]carbon molecule towards molecular N2 . Results show that the Si substituted derivative is effective in producing adducts with molecular nitrogen. Charge calculations and IRC trapping methods indicate that only the Si center of C17 Si and its (HOMO-1) level participate in N2 addition. The N-adduct so formed, is then found to spontaneously react with molecular H2 . The addition of two H2 molecules to the activated nitrogen molecule to give respective amine derivatives have also been studied. The successful generation of the precursor of NH3 by C17 Si lays a clear emphasis on its potentiality.