Abstract
13C and 17O chemical shifts and 55Mn,13C coupling constants of nine pentacarbonylmanganese complexes RMn(CO)5 (6–14), 13 tetracarbonylmanganese complexes RMn(CO)4PR3′ (15–27) and five tetracarbonylmanganacycle complexes (1a–e) were determined and are discussed in terms of σ-inductive substituent effects on axial and equatorial CO ligands. Linear correlations are observed between σI(R) and δ(13C) of equatorial CO ligands and δ(17O) of axial CO ligands, respectively. In the tetracarbonylmanganacycle complexes 1a–e the 17O chemical shifts of the axial (CO)a ligands exhibit the largest substituent effect (trans influence), they correlate with the rates log kobs of the demetalation reaction and the mechanistic implications are discussed. The 55Mn,13C coupling constants of the axial (CO)a ligands (144–159 Hz) likewise show a large and steady substituent dependence. © 1998 John Wiley & Sons, Ltd.
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