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Experimental and Computational Studies on the Reactivity of a Terminal Thorium Imidometallocene towards Organic Azides and Diazoalkanes
Author(s) -
Ren Wenshan,
Zhou Enwei,
Fang Bo,
Hou Guohua,
Zi Guofu,
Fang DeCai,
Walter Marc D.
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201406191
Subject(s) - intramolecular force , chemistry , reactivity (psychology) , medicinal chemistry , density functional theory , stereochemistry , base (topology) , bond length , molecule , organic chemistry , computational chemistry , medicine , alternative medicine , pathology , mathematical analysis , mathematics
The reaction of the base‐free terminal thorium imido complex [{η 5 ‐1,2,4‐(Me 3 C) 3 C 5 H 2 } 2 ThN(p‐tolyl)] ( 1 ) with p ‐azidotoluene yielded irreversibly the tetraazametallacyclopentene [{η 5 ‐1,2,4‐(Me 3 C) 3 C 5 H 2 } 2 Th{N( p ‐tolyl)NNN( p ‐tolyl)}] ( 2 ), whereas the bridging imido complex [{[η 5 ‐1,2,4‐(Me 3 C) 3 C 5 H 2 ]Th(N 3 ) 2 } 2 {μ‐N( p ‐tolyl)} 2 ][( n ‐C 4 H 9 ) 4 N] 2 ( 3 ) was isolated from the reaction of 1 with [( n ‐C 4 H 9 ) 4 N]N 3 . Unexpectedly, upon the treatment of 1 with 9‐diazofluorene, the NN bond was cleaved, an N atom was transferred, and the η 2 ‐diazenido iminato complex [{η 5 ‐1,2,4‐(Me 3 C) 3 C 5 H 2 } 2 Th{η 2 ‐[NN(p‐tolyl)]}{N(9‐C 13 H 8 )}] ( 4 ) was formed. In contrast, the reaction of 1 with Me 3 SiCHN 2 gave the nitrilimido complex [{η 5 ‐1,2,4‐(Me 3 C) 3 C 5 H 2 } 2 Th{NH( p ‐tolyl)}{N 2 CSiMe 3 }] ( 5 ), which slowly converted into [{η 5 ‐1,2,4‐(Me 3 C) 3 C 5 H 2 }{η 5 :κ‐ N ‐1,2‐(Me 3 C) 2 ‐4‐CMe 2 (CH 2 NNCHSiMe 3 )C 5 H 2 }Th{NH(p‐tolyl)}] ( 6 ) by intramolecular CH bond activation. The experimental results are complemented by density functional theory (DFT) studies.