Room temperature metathesis of aryl isocyanates and aromatic aldehydes catalyzed by group(IV) metal alkoxides: An experimental and computational study

Kumar, Akshai and Samuelson, Ashoka G (2010) Room temperature metathesis of aryl isocyanates and aromatic aldehydes catalyzed by group(IV) metal alkoxides: An experimental and computational study. In: Journal of Organometallic Chemistry, 695 (3). pp. 338-345.

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Abstract

Aromatic aldehydes and aryl isocyanates do not react at room temperature. However, we have shown for the first time that in the presence of catalytic amounts of group(IV) n-butoxide, they undergo metathesis at room temperature to produce imines with the extrusion of carbon dioxide. The mechanism of action has been investigated by a study of stoichiometric reactions. The insertion of aryl isocyanates into the metal n-butoxide occurs very rapidly. Reaction of the insertion product with the aldehyde is responsible for the metathesis. Among the n-butoxides of group(IV) metals, Ti((OBu)-Bu-n)(4) (8aTi) was found to be more efficient than Zr((OBu)-Bu-n)(4) (8aZr) and Hf((OBu)-Bu-n)(4) (8aHf) in carrying out metathesis. The surprisingly large difference in the metathetic activity of these alkoxides has been probed computationally using model complexes Ti(OMe)(4) (8bTi), Zr(OMe)(4) (8bZr) and Hf(OMe)(4) (8bHf) at the B3LYP/LANL2DZ level of theory. These studies indicate that the insertion product formed by Zr and Hf are extremely stable compared to that formed by Ti. This makes subsequent reaction of Zr and Hf complexes unfavorable.

Item Type:	Journal Article
Publication:	Journal of Organometallic Chemistry
Publisher:	Elsevier science
Additional Information:	Copyright for this article belongs to Elsevier science.
Keywords:	Aryl isocyanates; Aromatic aldehydes; Titanium n-butoxide; Titanium isopropoxide; Insertion; Metathesis
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	09 Feb 2010 11:27
Last Modified:	19 Sep 2010 05:54
URI:	http://eprints.iisc.ac.in/id/eprint/25511

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