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Density‐Functional Computation of 99 Ru NMR Parameters
Author(s) -
Bühl Michael,
Gaemers Sander,
Elsevier Cornelis J.
Publication year - 2000
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20000901)6:17<3272::aid-chem3272>3.0.co;2-e
Subject(s) - density functional theory , substituent , chemistry , relaxation (psychology) , nucleus , series (stratigraphy) , computation , electric field gradient , computational chemistry , electric field , crystallography , physics , stereochemistry , mathematics , quantum mechanics , algorithm , psychology , social psychology , paleontology , biology , microbiology and biotechnology
Gradient‐corrected and hybrid variants of density‐functional theory are used to compute the geometries and 99 Ru chemical shifts of RuO 4 , [RuCp 2 ], [K 4 Ru(CN) 6 ], [Ru 3 (CO) 12 ], [Ru(CO) 3 X 3 ] − (X=Cl, I), [Ru(CO) 2 Cl 4 ] 2− , [Ru(bipy) 3 ] 2+ , and [Ru(CO) 2 ( i Pr‐DAB)(X)(Y)] [XY=Cl 2 , I 2 , MeCl, MeI, or (SnMe 3 ) 2 ]. For this set of compounds, substituent effects on δ ( 99 Ru) are somewhat underestimated with the BPW91 pure density functional but are described well by the B3LYP hybrid functional, which can also be used to reproduce empirical trends in electric field gradients (EFGs) at the Ru nucleus qualitatively. In the [Ru(CO) 2 ( i Pr‐DAB)XY] series, trends in the computed EFGs parallel those in the observed 99 Ru NMR linewidths, in accordance with the quadrupolar relaxation mechanism expected for this nucleus. For this series of compounds, the use of X‐ray‐derived geometries affords a worse correlation between calculated EFGs and experimental linewidths than does the use of optimized geometries.