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Density functional computations of 99 Ru chemical shifts: relativistic effects, influence of the density functional, and study of solvent effects on fac —[Ru(CO) 3 I 3 ] −
Author(s) -
Autschbach Jochen,
Zheng Shaohui
Publication year - 2006
Publication title -
magnetic resonance in chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0749-1581
DOI - 10.1002/mrc.1885
Subject(s) - chemistry , density functional theory , solvent effects , chemical shift , computational chemistry , solvent , relativistic quantum chemistry , atomic physics , organic chemistry , physics
Solvent effects on the 99 Ru NMR chemical shift of the complex fac —[Ru(CO) 3 I 3 ] − are investigated computationally using density functional theory. Further, benchmark calculations of the 99 Ru shift for a set of ten Ru complexes have been performed in order to calibrate the computational model and to determine the importance of relativistic effects on the 99 Ru nuclear magnetic shielding and on the chemical shift. A computational model for fac —[Ru(CO) 3 I 3 ] − that includes both explicit solvent molecules and a continuum model is shown to yield the best agreement with experiment. Relativistic corrections are shown to be of minor importance for determining 99 Ru chemical shifts. On the other hand, the nature of the density functional is of importance. In agreement with literature data for ligand trends of 99 Ru chemical shifts, the chemical shift range for different solvents is also best reproduced by a hybrid functional. Copyright © 2006 John Wiley & Sons, Ltd.