Rhodium-calix[4]pyrrole and rhodium-tetraphenyl porphyrin: preparation, surface grafting and their catalytic application in nitro-benzene reduction

Abstract

Rhodium containing macromolecules calix[4]pyrrole (RhCP) and tetraphenyl porphyrin (RhTPP) were prepared and grafted on the surface of functionalised molecular sieve materials. ¹H and ¹³C NMR, CHNS and mass spectral analyses were used for the structural elucidation of homogeneous organometallic complexes.¹H NMR and CHNS analyses confirm the formation of calix[4]pyrrole (CP) and tetraphenyl porphyrin (TPP). The introduction of rhodium ions into the macromolecule is well evident from the disappearance of the ¹H NMR signal characteristic of N–H proton (7.1 ppm in CP and −2.74 ppm in TPP). Furthermore the formation of RhCP and RhTPP complexes is confirmed using CHNS and mass spectral analysis; the data are in line with theoretically calculated values. The grafting of RhCP and RhTPP on a diamino functionalised SBA-15 support was confirmed through low angle XRD, ¹³C MAS-NMR and SEM-EDAX analysis. Both homogeneous and heterogeneous catalysts were utilized for nitrobenzene reduction. RhCP and RhTPP heterogenized on SBA-15-F showed complete conversion of nitrobenzene with exclusive formation of aniline as a product. The catalytic activities were retained in both the systems even after several runs.