Experimental and Computational Studies on the Reactivity of a Terminal Thorium Imidometallocene towards Organic Azides and Diazoalkanes1. (28th August 2014)

• Record Type: Journal Article
• Authors: Ren, Wenshan; Zhou, Enwei; Fang, Bo; Hou, Guohua; Zi, Guofu; Fang, De‐Cai; Walter, Marc D.
• Is Part Of: Angewandte Chemie. Volume 126:Number 42(2014)
• Page Start: 11492
• Page End: 11496
• Publication Date: 2014-08-28
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201406191
• Languages: English
• ISSNs: 0044-8249

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The reaction of the base‐free terminal thorium imido complex [{η<sup>5</sup>‐1, 2, 4‐(Me<sub>3</sub>C)<sub>3</sub>C<sub>5</sub>H<sub>2</sub>}<sub>2</sub>ThN(p‐tolyl)] (<bold>1</bold>) with <italic>p</italic>‐azidotoluene yielded irreversibly the tetraazametallacyclopentene [{η<sup>5</sup>‐1, 2, 4‐(Me<sub>3</sub>C)<sub>3</sub>C<sub>5</sub>H<sub>2</sub>}<sub>2</sub>Th{N(<italic>p</italic>‐tolyl)NNN(<italic>p</italic>‐tolyl)}] (<bold>2</bold>), whereas the bridging imido complex [{[η<sup>5</sup>‐1, 2, 4‐(Me<sub>3</sub>C)<sub>3</sub>C<sub>5</sub>H<sub>2</sub>]Th(N<sub>3</sub>)<sub>2</sub>}<sub>2</sub>{μ‐N(<italic>p</italic>‐tolyl)}<sub>2</sub>][(<italic>n</italic>‐C<sub>4</sub>H<sub>9</sub>)<sub>4</sub>N]<sub>2</sub> (<bold>3</bold>) was isolated from the reaction of <bold>1</bold> with [(<italic>n</italic>‐C<sub>4</sub>H<sub>9</sub>)<sub>4</sub>N]N<sub>3</sub>. Unexpectedly, upon the treatment of <bold>1</bold> with 9‐diazofluorene, the NN bond was cleaved, an N atom was transferred, and the η<sup>2</sup>‐diazenido iminato complex [{η<sup>5</sup>‐1, 2, 4‐(Me<sub>3</sub>C)<sub>3</sub>C<sub>5</sub>H<sub>2</sub>}<sub>2</sub>Th{η<sup>2</sup>‐[NN(p‐tolyl)]}{N(9‐C<sub>13</sub>H<sub>8</sub>)}] (<bold>4</bold>) was formed. In contrast, the reaction of <bold>1</bold> with Me<sub>3</sub>SiCHN<sub>2</sub> gave the nitrilimido complex [{η<sup>5</sup>‐1, 2, 4‐(Me<sub>3</sub>C)<sub>3</sub>C<sub>5</sub>H<sub>2</sub>}<sub>2</sub>Th{NH(<italic>p</italic>‐tolyl)}{N<sub>2</sub>CSiMe<sub>3</sub>}] (<bold>5</bold>), which slowly converted into [{η<sup>5</sup>‐1, 2, 4‐(Me<sub>3</sub>C)<sub>3</sub>C<sub>5</sub>H<sub>2</sub>}{η<sup>5</sup>:κ‐<italic>N</italic>‐1, 2‐(Me<sub>3</sub>C)<sub>2</sub>‐4‐CMe<sub>2</sub>(CH<sub>2</sub>NNCHSiMe<sub>3</sub>)C<sub>5</sub>H<sub>2</sub>}Th{NH(p‐tolyl)}] (<bold>6</bold>) by intramolecular CH bond activation. The experimental results are complemented by density functional theory (DFT) studies.</p> </abstract>