The role of Cr, Mo and W in the electronic delocalization and the metal-ring interaction in metallocene complexes

• Published in: New journal of chemistry Vol. 42; no. 7; pp. 5334 - 5344
• Main Authors: Arias-Olivares, David, Páez-Hernández, Dayán, Islas, Rafael
• Format: Journal Article
• Language: English
• Published: 2018
• ISSN: 1144-0546; 1369-9261
• DOI: 10.1039/c8nj00510a

Metal influence over triple-decker, sandwich-like and pyramidal structured benzenes was studied by means of Energy Decomposition Analysis (Morokuma-Ziegler), combined with Extended Transition State Natural Orbitals for Chemical Valence, finding that metal-ring bonding was a covalent contribution of about 60% due to the bonding interaction between d xz and d yz , d x 2 − y 2 and d xy orbitals with p z orbitals, respectively, adapted by symmetry in the ring, to form π and δ bonding interactions. Finally, an important amount of electron density between the ring and the metal was found. This has a key role in the electron delocalization in this zone. This electronic delocalization was analysed via Induced Magnetic Field and Nucleus-Independent Chemical Shift calculations, finding a pattern between metal atomic radii and shielding tensor. Furthermore, similar behaviour for Mo and W, in the enhancement of the diatropic magnetic response, was displayed while Cr had a slightly lower diatropic character. Metal influence over triple-decker, sandwich-like and pyramidal structured benzenes was studied by means of energy decomposition analysis (Morokuma-Ziegler), combined with extended transition state natural orbitals for chemical valence, and Nucleus Independent Chemical Shift descriptors.