Übergangsmetallbenz - in-Komplexe. Dynamisches Verhalten von [Ta(C6H5)4(C6H4)a(Li • OC4H10)3] / Transition Metal Benzyne Complexes. Fluxional Behaviour of [TA(C6H5)4(C6H4)2(Li·OC4H10)3]

Sarry, Brigitte; Schaffernicht, Rolf

doi:10.1515/znb-1981-1009

Cited by 12 publications

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References 11 publications

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“…Interestingly, only two other dibenzyne complexes have been previously structurally characterized: namely, [Li(THF) 3 ] 2 [LiCl(THF) 2 ] 2 [Li(THF) 2 ] 4 [Ta(η 2 -C 6 H 4 ) 2 Ph 4 ] 2 and [Li(THF)] 4 [LiPh(THF)][Nb(η 2 -C 6 H 4 ) 2 Ph 3 ] . However, a few other transition-metal dibenzynes have been synthesized but not characterized by X-ray crystallography, including [Li(Et 2 O)] 3 [W( p -Tol) 4 (η 2 -C 6 H 3 CH 3 ) 2 ]. − …”

Section: Resultssupporting

confidence: 79%

Synthesis and Reactivity of a U(IV) Dibenzyne Complex

et al. 2016

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Reaction of UCl4 with 6 equiv of 2-Li-C6H4CH2NMe2 affords the U(IV) dibenzyne complex [Li]2[U(2,3-C6H3CH2NMe2)2(2-C6H4CH2NMe2)2] (1), which can be isolated as a dark blue solid in 40% yield. Complex 1 represents a rare example of a structurally characterized dibenzyne complex, and its solid-state metrical parameters suggest that the two benzyne ligands are best described with the dianionic metallacyclopropene resonance form. The reactivity of 1 with a variety of electrophiles and oxidants, including benzophenone, 1-azidoadamantane, and benzonitrile, was also explored. Reaction of 1 with 2 equiv of benzophenone affords the insertion product [Li][U(2-C6H3CH2NMe2-3-COPh2)2(2-C6H4CH2NMe2)] (3) as a red-orange solid in 61% yield, concomitant with formation of 1 equiv of 2-Li-C6H4CH2NMe2. Reaction of 1 with 2 equiv of PhCN also affords an insertion product, [Li][Li(Et2O)][U(2,3-C6H3CH2NMe2)(2-C6H3CH2NMe2-3-C(Ph)N)(2-C6H4CH2NMe2)2] (4), as a green-brown crystalline solid in 21% yield. In an attempt to oxidize 1 to U(VI), the reaction of 1 with 2 equiv of AdN3, in the presence of 2 equiv of 12-crown-4, was probed. This reaction only yields the U(IV) insertion product [Li(12-crown-4)2][Li][U(2-C6H3CH2NMe2-3-(N-NN-Ad))2(2-C6H4CH2NMe2)2] (5) as a red crystalline solid in 42% yield. No evidence for the formation of a U(VI) imido complex is observed in the reaction mixture.

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Section: Resultssupporting

confidence: 79%

Synthesis and Reactivity of a U(IV) Dibenzyne Complex

et al. 2016

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“…The structures of both ions are very similar and quite regular trigonal prismatic. [18] [TaA C H T U N G T R E N N U N G (C 6 À were initially observed in solution by NMR spectroscopy, [19,20] subsequently they were characterized crystallographically [10] and found to have a trigonal-prismatic structure.…”

Section: Niobium Complexes: [Nba C H T U N G T R E N N U N G (Ch 3 ) 6 ]mentioning

confidence: 99%

Homoleptic Organometallic Anions of Ti, Zr, Hf, and Nb

El‐Kurdi

Seppelt

2011

Chemistry A European J

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Reactions of C(6)H(5)Li and 4-CH(3)C(6)H(4)Li with halides of Ti, Ir, Hf, and Nb lead to the formation of homoleptic organometallic anions of these metals. Owing to their thermal instability and their sensitivity towards H(2) O and O(2) , these compounds are characterized by single-crystal structure determinations at low temperature, whereas other physical data could only be obtained occasionally. Three pentacoordinate complex anions [Ti(C(6)H(5))(5)](-), [Ti(4-CH(3)C(6)H(4))(5)](-), and [Zr(C(6)H(5))(5)](-) have square-pyramidal structures that display only slight deviations from the ideal geometry, in contrast to the already known structures of [Ti(CH(5))(5)](-). The hexacoordinate complex anions [Zr(C(6)H(5))(6)](2-), [Zr(4-CH(3)C(6)H(4))(6)](2-), [Nb(C(6)H(5))(6)](2-), and [Nb(4-CH(3)C(6)H(4))(6)](2-) all have trigonal-prismatic structures, in accord with the known hexamethyl complex dianions. In contrast, the hexacoordinate complex anion [Hf(C(6)H(5))(6)](2)(-) has an octahedral or close to octahedral structure, in contrast to the known trigonal-prismatic structures of [Ta(C(6)H(5))(6)](-) and [Ta(4-CH(3)C(6)H(4))(6) (-). A qualitative explanation for this structural variability is given.

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Metall‐Komplexe mit kleinen Cycloalkinen und Arinen

Bennett

Schwemlein

1989

Angewandte Chemie

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Cyclooctin ist das kleinste unsubstituierte Cycloalkin, das in freier Form isoliert werden kann, und es ist gegenüber Übergangsmetall‐Komplexen reaktiver als acyclische Alkine. Kleinere Cycloalkine wie Cycloheptin, Cyclohexin, Dehydrobenzol und Cyclopentin, die in freier Form instabil sind, können durch Koordination an einkernige, elektronenreiche Fragmente mit Übergangsmetallen, z. B. [ZrCp2(PMe3)] und M(PR3)2 (M = Ni, Pt), oder durch Bildung von zwei‐ oder mehrkernigen Metall‐Komplexen, beispielweise [Os3H2(CO)9(C6H4)] und [Pt2(μ‐PPh2)(μ‐C5H6)(PPh3)3], stabilisiert werden. Die Alkine können zwei bis vier π‐Elektronen an das Metallzentrum abgeben, wobei für die frühen Übergangsmetalle die höhere Anzahl bevorzugt wird. In die Cycloalkin‐Metall‐ und Arin‐Metall‐Bindungen der einkernigen Komplexe lassen sich leicht Moleküle einschieben, die CO‐, CC‐, CC‐ und CN‐Bindungen enthalten; dies ist eine Eigenschaft, die in der organischen Synthese nützlich sein kann. Das hochgradig ungesättigte 1,2,4,5‐Tetradehydrobenzol fungiert in [{Ni(Cy2PCH2CH2PCy2)}2‐(μ‐C6H2)] als verbrückender Ligand zwischen zwei Metallzentren.

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Übergangsmetallbenz - in-Komplexe. Dynamisches Verhalten von [Ta(C₆H₅)₄(C₆H₄)a(Li • OC₄H₁₀)₃] / Transition Metal Benzyne Complexes. Fluxional Behaviour of [TA(C₆H₅)₄(C₆H₄)₂(Li·OC₄H₁₀)₃]

Abstract: Abstract Products of the reaction between MBr5 and PhLi are proved to be benzyne complexes [M(C6H5)4(CeH4)2(Li · OC4H10)n], (M = Nb, Ta, W). Analysis of the temperature dependent 1 H and 7 Li NMR Spectra of [Ta(C6H5)4(C6… Show more

Cited by 12 publications

References 11 publications

Synthesis and Reactivity of a U(IV) Dibenzyne Complex

Synthesis and Reactivity of a U(IV) Dibenzyne Complex

Homoleptic Organometallic Anions of Ti, Zr, Hf, and Nb

Metall‐Komplexe mit kleinen Cycloalkinen und Arinen

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