Novel trans iodo(2-(N-alkylsulfamoyl)phenyl)bis(-triphenylphosphine palladium) complexes: Synthesis, mass spectrometry, X-ray structural description, steric map, near infrared analyses and catalytic activities evaluation

2-iodo-N-ethylbenzenesulfonamide and 2-iodo-N-isopropylbenzenesulfonamide are used to prepare two novel palladium(II) complexes (4 and 5) by oxidative addition starting from Pd(PPh3)4. The desired complexes are fully characterized by 1H, 13C, 31P NMR and near infrared spectroscopy. Electron spray ionization mass spectrometry analyses showed identical fragmentation process of the complexes starting by the iodine cleavage. The molecular structures of the complexes 4 and 5 are confirmed by X-ray diffraction analysis. The crystal packing of these complexes are stabilized by the presence of hydrogen bonds established between oxygen and hydrogen atoms of the sulfonamide groups. In addition, Hirshfeld surface mapped over dnorm, Shape index and molecular electrostatic potential were used to describe the short interactions and electron reach domains. The analyses of molecular fingerprints reveal similar percentage of H···H (∼67%), H···C/C···H (∼23%), H···I/I···H (∼5%) and H···O/O···H (∼4.5%) contacts in 4 and 5. The valuation of the percentage of buried volume (%VBur) of these ligands shows that the N-ethyl- and N-isopropylbenzenesulfonamide substituents took around 30% share of the palladium coordination sphere. Finally, the catalytic activities of these new palladium complexes are evaluated in cyclopropanation of styrene and in atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA). The results showed that trans cyclopropane was obtained as major product independently to the tested catalyst. In polymerization reaction, the catalysts show moderate activity and did not induce a controlled polymerization of MMA.