title: Experimental and computational studies on the reactivity of a terminal thorium imidometallocene towards organic azides and diazoalkanes.
abstract: The reaction of the base-free terminal thorium imido complex [{η(5)-1,2,4-(Me3C)3C5H2}2Th=N(p-tolyl)] (1) with p-azidotoluene yielded irreversibly the tetraazametallacyclopentene [{η(5)-1,2,4-(Me3C)3C5H2}2Th{N(p-tolyl)N=N-N(p-tolyl)}] (2), whereas the bridging imido complex [{[η(5)-1,2,4-(Me3C)3C5H2]Th(N3)2}2{μ-N(p-tolyl)}2][(n-C4H9)4N]2 (3) was isolated from the reaction of 1 with [(n-C4H9)4N]N3. 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-(Me3C)3C5H2}2Th{η(2)-[N=N(p-tolyl)]}{N=(9-C13H8)}] (4) was formed. In contrast, the reaction of 1 with Me3SiCHN2 gave the nitrilimido complex [{η(5)-1,2,4-(Me3C)3C5H2}2Th{NH(p-tolyl)}{N2CSiMe3}] (5), which slowly converted into [{η(5)-1,2,4-(Me3C)3C5H2}{η(5):κ-N-1,2-(Me3C)2-4-CMe2(CH2NN=CHSiMe3)C5H2}Th{NH(p-tolyl)}] (6) by intramolecular C-H bond activation. The experimental results are complemented by density functional theory (DFT) studies.
authors.affiliation: Department of Chemistry, Beijing Normal University, Beijing 100875 (China); College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715 (China).
authors.forename: Wenshan
authors.initials: W
authors.lastname: Ren
authors.forename: Enwei
authors.initials: E
authors.lastname: Zhou
authors.forename: Bo
authors.initials: B
authors.lastname: Fang
authors.forename: Guohua
authors.initials: G
authors.lastname: Hou
authors.forename: Guofu
authors.initials: G
authors.lastname: Zi
authors.forename: De-Cai
authors.initials: DC
authors.lastname: Fang
authors.forename: Marc D
authors.initials: MD
authors.lastname: Walter
keywords: cycloaddition; diazoalkanes; imido complexes; organic azides; thorium