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Issue 10, 2015

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

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Abstract

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.

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

Supplementary files

Article information


Submitted
24 Jun 2015
Accepted
17 Jul 2015
First published
20 Jul 2015

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2015,6, 5456-5465
Article type
Edge Article

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 and J. Basset, Chem. Sci., 2015, 6, 5456 DOI: 10.1039/C5SC02276B

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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