Chemie der schweren Carben-Analogen R2M (M  Si, Ge, Sn) XIX . Reaktionen von stabilem Diaminogermylen und -stannylen Me2Si(tBuN)2 M (M  Ge, Sn) mit organischen Aziden

Klein, Beatrix; Neumann, Wilhelm P.

doi:10.1016/0022-328x(94)87045-4

Cited by 23 publications

(3 citation statements)

References 21 publications

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“…Complex 1 reacted in a [2+3] cycloaddition reaction with p-azidotoluene to give the tetraazametallacyclopentene [{h 5 -1,2,4-(Me 3 C) 3 C 5 H 2 } 2 Th{N(p-tolyl)N=NÀN(p-tolyl)}] (2) with quantitative conversion (Scheme 1). Similar reactivity was observed for aluminum, [13] germanium, [14] and osmium [15] imido compounds. However, in contrast to those of zirconium [6e] and niobium [7c] imido complexes, the reaction of 1 with organic azides is irreversible, as demonstrated by variable-temperature 1 H NMR spectroscopic investigations (20-100 8C).…”

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confidence: 76%

Experimental and Computational Studies on the Reactivity of a Terminal Thorium Imidometallocene towards Organic Azides and Diazoalkanes

et al. 2014

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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.

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confidence: 76%

Experimental and Computational Studies on the Reactivity of a Terminal Thorium Imidometallocene towards Organic Azides and Diazoalkanes

et al. 2014

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“…The formation of 4 may undergo a possible germanimine R 1 Ge(NTMS)–GeL 3 , accompanied by a migration of the −GeL 3 group from the Ge GeN atom to the N GeN atom, showing a reactive Ge–Ge bond in compound 1 . This reaction mode contrasts markedly with the ubiquitous formation of stable GeN species or azagermanes containing Ge 2 N, GeN 4 , and Ge 2 N 2 rings . A similar reaction was not reported in the alkylgermyl germylene 2,6-Mes 2 C 6 H 3 Ge–Ge t Bu 3 (Mes = mesityl) system with the strong electron-donating −Ge t Bu 3 substituent .…”

Section: Resultsmentioning

confidence: 73%

Formation of Alkynylgermyl-Substituted Germylenes via a Catenation of Ge Atoms

et al. 2020

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Reactions of amidinate-stabilized germylene chlorides R1Ge(:)Cl (R1 = PhC(NtBu)2) and R2Ge(:)Cl (R2 = PhC(NCy)2, Cy = cyclohexanyl) with trimethylsilylethynyl lithium salt (LLi, L = −CCTMS) afforded alkynylgermyl-substituted germylenes R1(:)Ge-GeL3 (1) and [R2GeL2]2Ge(:) (2), respectively. Both of them may undergo the formation of Ge–Ge single bonds with a concomitant 1,2-shift of ethynyl groups. DFT calculations determined the reaction pathways where two possible intermediates (:)GeL2 and RGe(:)L (R = R1, R2) are proposed, which were consistent with the trapping reactions of (:)GeL2 toward IAr–(:)GeL2 (3, IAr = :C{N(Ar)CH}2, Ar = 2,6-iPr2C6H3). The reaction of 1 with N3TMS gave a new aminogermylene R1(:)Ge–N(TMS)-GeL3 (4), indicating a reactive Ge–Ge bond.

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“…In related work, the reactions of various stable germylenes and stannylenes with organic azides have been examined, , and the reaction of the N-heterocyclic carbene analogue of 1 with Me 3 SiN 3 was recently reported . Roesky and co-workers observed that the novel Al(I) compound [HC(CMeNAr) 2 ]Al reacts with Me 3 SiN 3 or Ph 3 SiN 3 to give the corresponding tetrazolines 8 as the only products (Ar = 2,6-di-isopropylbenzene) (Chart ) .…”

Section: Introductionmentioning

confidence: 99%

Reactions of Stable Silylenes with Organic Azides

et al. 2005

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Reactions of N-heterocyclic stable silylenes 1 and 2 with various organic azides have been studied. Silylene 1 reacts with RN3 (R = phenyl, p-tolyl, Ph3C, Ph3Si) to yield the spirocyclic silatetrazolines 11−14. Silylene 2 reacts similarly to give derivatives 16−19, except that with R = p-tolyl a small amount of a μ2-azine-bridged tricyclic product 20 is also formed. The products are consistent with reactions proceeding through an unstable iminosilane intermediate. A definitive crystal structure for 2 is reported.

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Chemie der schweren Carben-Analogen R2M (M  Si, Ge, Sn) XIX . Reaktionen von stabilem Diaminogermylen und -stannylen Me2Si(tBuN)2 M (M  Ge, Sn) mit organischen Aziden

Cited by 23 publications

References 21 publications

Experimental and Computational Studies on the Reactivity of a Terminal Thorium Imidometallocene towards Organic Azides and Diazoalkanes

Experimental and Computational Studies on the Reactivity of a Terminal Thorium Imidometallocene towards Organic Azides and Diazoalkanes

Formation of Alkynylgermyl-Substituted Germylenes via a Catenation of Ge Atoms

Reactions of Stable Silylenes with Organic Azides

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