Tris-{Hydridotris(1-pyrazolyl)borato}lanthanide complexes: synthesis, spectroscopy, crystal structure and bonding properties.

Complexes of trivalent lanthanides (Ln) with the hydridotris(1-pyrazolyl)borato (Tp) ligand, Ln[n3-HB(N2C3H3)3]3 (LnTp3), have been subjected to a joint experimental-theoretical analysis. X-ray diffraction experiments have been performed on CeTp3, NdTp3, SmTp3, TbTp3. Density Functional Theory (DFT) calculations have been carried out for all the 15 LnTp3 complexes. They extended the X-ray diffraction data available on eight LnTp3 compounds and facilitated a straightforward interpretation of trends in the structural parameters. As a result of the joint analysis, a significant steric strain in the equatorial coordination sites of the 9-coordinate structures has been recognised. Trends in the bonding properties have been elucidated by energy decomposition and Quantum Theory of Atoms in Molecules (QTAIM) analysis of the electron density distribution. These results revealed the major electrostatic character of the Ln…Tp bonding and fine variation of charge transfer effects across the Ln row.

APOSTOLIDIS C.;  KOVACS Attila;  MORGENSTERN Alfred;  REBIZANT J.;  WALTER Olaf; 

2021-10-01

MDPI

JRC124831

2304-6740 (online),   

https://www.mdpi.com/2304-6740/9/6/44,    https://publications.jrc.ec.europa.eu/repository/handle/JRC124831,   

10.3390/inorganics9060044 (online),