13C, 17O and 55Mn NMR studies on substituted manganese carbonyl complexes. A contribution to the mechanism of demetalation reactions
✍ Scribed by Daniel Rentsch; Lilan Nill; Wolfgang von Philipsborn; D. Richard Sidler; Philip J. Rybczynski; Philip DeShong
- Publisher
- John Wiley and Sons
- Year
- 1998
- Tongue
- English
- Weight
- 297 KB
- Volume
- 36
- Category
- Article
- ISSN
- 0749-1581
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✦ Synopsis
13C and 17O chemical shifts and 55Mn,13C coupling constants of nine pentacarbonylmanganese complexes (6È14), 13 tetracarbonylmanganese complexes (15È27) and Ðve tetra-RMn(CO) 5 RMn(CO) 4 PR 3 @ carbonylmanganacycle complexes (1aÈe) were determined and are discussed in terms of p-inductive substituent e †ects on axial and equatorial CO ligands. Linear correlations are observed between and d(13C) of equatorial p I (R) CO ligands and d(17O) of axial CO ligands, respectively. In the tetracarbonylmanganacycle complexes 1aÈe the 17O chemical shifts of the axial ligands exhibit the largest substituent e †ect (trans inÑuence), they correlate with (CO) a the rates of the demetalation reaction and the mechanistic implications are discussed. The 55Mn,13C coup-log k obs ling constants of the axial ligands (144È159 Hz) likewise show a large and steady substituent dependence. (CO)