Transition Metal NMR Spectroscopy. One-bond 103Rh,15N coupling constants of axial and equatorial ligands in rhodoximes
✍ Scribed by Gudrun Hopp Rentsch; Wiktor Kozminski; Wolfgang von Philipsborn Fioretta Asaro; Giorgio Pellizer
- Publisher
- John Wiley and Sons
- Year
- 1997
- Tongue
- English
- Weight
- 219 KB
- Volume
- 35
- Category
- Article
- ISSN
- 0749-1581
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✦ Synopsis
The 103Rh,15N coupling constants and 15N chemical shifts of rhodoximes XRhIII(Hdmg) 2 L (Hdmg = dimethylglyoximate, or pyridine, X = halide, alkyl, haloalkyl) were extracted from gradient-L = PPh 3 selected (1H,15N)-HSQC experiments. Coupling between rhodium and the equatorial oxime nitrogens is large (18-21 Hz) and shows little sensitivity to the nature of the cis-oriented ligands X and L. In contrast, coupling between rhodium and the axial pyridine nitrogen is small (6-9 Hz) for X = alkyl but increases to 16-18 Hz in the halide complexes ("trans inÑuenceÏ). The structural implications are discussed in conjunction with x-ray data.