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Steric and Electronic Effects on the 103 Rh NMR Chemical Shifts of Rh I (cyclooctadiene) Compounds Bearing N‐Donor Ligands
Author(s) -
Donkervoort Johannes G.,
Bühl Michael,
Ernsting Jan Meine,
Elsevier Cornelis J.
Publication year - 1999
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199901)1999:1<27::aid-ejic27>3.0.co;2-4
Subject(s) - chemistry , steric effects , chemical shift , electronic effect , nuclear magnetic resonance spectroscopy , bond length , density functional theory , computational chemistry , crystallography , stereochemistry , crystal structure
In order to study electronic and steric effects on δ( 103 Rh), the 103 Rh‐NMR spectra of a series of [Rh(cod)L 2 ] complexes (with L = nitrogen, oxygen, or chloride) have been measured by gradient‐enhanced HMQC ( 1 H, 103 Rh) NMR spectroscopy. Density functional computations of representative examples have been performed at the GIAO‐B3LYP level of theory. The obtained experimental values of 103 Rh shifts fit the generally observed trend of coordinating ligands in the first coordination sphere of the metal: P < N < O. Calculated 103 Rh shifts agreed to within 8 % with experimental values. The computational results indicate that the Rh–N bond distance has a larger influence on the chemical shift than the N–Rh–N angle.