Well-defined silica supported aluminum hydride: another step towards the utopian single site dream

B. Werghi, A. Bendjeriou-Sedjerari, J. Sofack-Kreutzer, A. Jedidi, E. Abou-Hamad, L. Cavallo, J.-M. Basset
Chem. Sci., 6 (10), 5456-5465, (2016)




​Reaction of triisobutylaluminum with SBA15700 at room temperature occurs by two parallel pathways involving either silanol or siloxane bridges. It leads to the formation of a well-defined bipodal [([triple bond, length as m-dash]SiO)2Al–CH2CH(CH3)2] 1a, silicon isobutyl [[triple bond, length as m-dash]Si–CH2CH(CH3)2] 1b and a silicon hydride [[triple bond, length as m-dash]Si–H] 1c. Their structural identity was characterized by FT-IR and advanced solid-state NMR spectroscopies (1H, 13C, 29Si, 27Al and 2D multiple quantum), elemental and gas phase analysis, and DFT calculations. The reaction involves the formation of a highly reactive monopodal intermediate: [[triple bond, length as m-dash]SiO–Al–[CH2CH(CH3)2]2], with evolution of isobutane. This intermediate undergoes two parallel routes: transfer of either one isobutyl fragment or of one hydride to an adjacent silicon atom. Both processes occur by opening of a strained siloxane bridge, [triple bond, length as m-dash]Si–O–Si[triple bond, length as m-dash] but with two different mechanisms, showing that the reality of “single site” catalyst may be an utopia: DFT calculations indicate that isobutyl transfer occurs via a simple metathesis between the Al-isobutyl and O–Si bonds, while hydride transfer occurs via a two steps mechanism, the first one is a β-H elimination to Al with elimination of isobutene, whereas the second is a metathesis step between the formed Al–H bond and a O–Si bond. Thermal treatment of 1a (at 250 °C) under high vacuum (10−5 mbar) generates Al–H through a β-H elimination of isobutyl fragment. These supported well-defined Al–H which are highly stable with time, are tetra, penta and octa coordinated as demonstrated by IR and 27Al–1H J-HMQC NMR spectroscopy. All these observations indicate that surfaces atoms around the site of grafting play a considerable role in the reactivity of a single site system.


 DOI: 10.1039/C5SC02276B


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