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Dihydrogen, dihydride and in between: NMR and structural properties of iron group complexes
Tabulating the structures and characteristic NMR properties of 17 iron complexes, 98 ruthenium complexes and 70 osmium complexes that contain dihydrogen or compressed dihydride ligands reveals a variety of trends. The H{single bond}H bond lengths increase from similar Fe(II) to Ru(II) to Os(II) complexes. Iron(II) displays a narrow range of H{single bond}H distances for stable complexes. Electronegative atoms Cl and O, when attached on the metal trans to the dihydrogen ligand, result in elongation of the H{single bond}H bond relative to more electropositive atoms H, C, P and N. The family of cyclopentadienyl ligands also causes this elongating effect. The dihydrogen ligands with short H{single bond}H distances and weak interactions with the metal, especially on iron and ruthenium are in the fast spinning regime. One exception is the biporphyrin complex of ruthenium with the side-on bridging H2 ligand which has an H{single bond}H distance of 118 pm but is in the fast spinning regime. There are some ruthenium complexes with H{single bond}H distances greater than 110 pm that are in the slow motion regime and several complexes of osmium with H{single bond}H distances greater than 130 pm that are in this regime. The large JHH due to quantum mechanical exchange coupling are observable for some of these osmium complexes with H{single bond}H distances in the range of 140-160 pm. The dihydrogen ligands in many complexes appear to have librational motions or other motions that place them in the intermediate motion regime. New equations to correlate JHD with H{single bond}H distances for ruthenium dihydrogen complexes and for osmium dihydrogen complexes are introduced here.
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Reference£º
Chiral Catalysts,
Chiral catalysts – SlideShare