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24.2H: Dihydrogen

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    34587
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    Metal dihydrogen complexes

    The simplest variant of a σ−complex contains a dihydrogen ligand. The first dihydrogen complex was isolated by Kubas, after which many new ones were reported.

    Quite expectedly, the dihydrogen moiety bound to a metal in a σ−complex is found to be more acidic (pKa = 0 − 20) when compared to the free dihydrogen molecule (pKa = 35). It is interesting to note that the pKa change associated with the binding of dihydrogen to a metal in a σ−complex relative to that of the free H2 molecule is significantly larger than the change associated with binding of H2O to metal. Owing to this inherent acidity, the deprotonation of the metal bound dihydrogen moiety by a base can thus be appropriately employed for heterolytic activation of the dihydrogen moiety as illustrated below.

    The dihydrogen complexes of metals are often referred to as nonclassical hydrides. The electron rich π basic metals are anticipated to split the metal bound dihydrogen moieties resulting in classical dihydride complexes. Along the same line of thinking, the electron deficient and less π basic metal would tend to stabilize a dihydrogen complex. The dihydrogen complexes can also be characterized by the X ray diffraction as well as neutron diffraction methods. In IR spectrum, the metal bound H−H stretch appear in the range (2300 − 2900) cm−1 while in the 1H NMR spectrum the same appear between 0 to −10 ppm as a broad peak. The dihydrogen complexes are often characterized by isotopic labeling studies of metal bound H−D moiety that shows a coupling constant of 20 – 34 Hz as supposed to 43 Hz observed in case of the free H−D molecule.


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