Dimerization of titanacyclocumulenes to titanium substituted radialenes: synthesis, stability and reactions of five-membered titanacyclocumulenes with a coupling of two 1,4-diphenyl-1,3-butadiyne between two titanocene molecules to radialene-like fused titanacyclopentadiene compounds

Pellny, Paul‐Michael; Burlakov, Vladimir V.; Peulecke, Normen; Baumann, Wolfgang; Spannenberg, Anke; Kempe, Rhett; Francke, Volkhard; Rosenthal, Uwe

doi:10.1016/s0022-328x(98)01114-0

Cited by 36 publications

(36 citation statements)

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“…Complexes of transoid butadiynes coordinated by two titanium atoms are usually obtained either from butadiynes and Ti II precursors [29][30][31] or from acetylides and Ti III halides. [32] In the latter case, C-C coupling of two phenylacetylide moieties in a titanocene complex was observed.…”

Section: Resultsmentioning

confidence: 99%

Examples of Different Reactions of Benzylsulfanyl‐Substituted Alkynes with Selected Complexes of Ti^II and Co^I

et al. 2013

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Reactions of the group 4 metallocene alkyne complexes [Cp 2 M(L)(btmsa)] (Cp = η 5 -cyclopentadienyl = η 5 -C 5 H 5 , btmsa = η 2 -Me 3 SiC 2 SiMe 3 ; 1: M = Ti, L = none; 2: M = Zr, L = pyridine) and of the [(triphos)Co I ] moiety [triphos = 1,1,1tris(diphenylphosphanylmethyl)ethane] with the benzylsulfanyl-substituted acetylenes PhCH 2 S-C 2 -SCH 2 Ph (3) and PhCH 2 S-C 2 -SFmoc (4) (Fmoc = fluorenylmethoxycarbonyl) have been investigated. Complex 1 reacted with 3 to give a mixture of a violet solid and [Cp 2 Ti(SCH 2 Ph) 2 ] (5). Subsequently, the violet solid transformed in toluene at 70°C into the dinuclear complex [(Cp 2 Ti) 2 (μ-κ 2 -κ 2 -BnSC 4 SBn)] (6) displaying two [Cp 2 Ti] moieties bridged by a 1,4-bis(benzylsulfanyl)-1,3-butadiyne in the trans configuration. Complex 6 was further degraded in toluene at 100°C to the tetranuclear cluster [CpTiS] 4 (7). Similar reactivity was deduced indirectly for the reaction partners 1/4 and 2/3. For Co I , the side-on[a] Leibniz-

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Section: Resultsmentioning

confidence: 99%

Examples of Different Reactions of Benzylsulfanyl‐Substituted Alkynes with Selected Complexes of Ti^II and Co^I

et al. 2013

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“…This coordination changes the electronic structure of cumulenes; nevertheless, for some of the complexes 191, dimerisaition to give radialene (192) has been observed. 319 This reaction is also characteristic of purely organic strained cumulenes. 320 Metallacyclocumulenes have been investigated by X-ray diffraction analysis.…”

Section: Cyclic Butatrienesmentioning

confidence: 91%

Organic molecules with abnormal geometric parameters

Komarov¹

2001

Russ. Chem. Rev.

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“…In former investigations with buta‐1,3‐diynes, several products could be isolated that were built by single ( E ) or double ( transoid : F , cisoid : G ) complexation, cleavage ( H ), or coupling of the ligand ( I – L ; Figure 4). 14 We could show that the metallacyclopenta‐2,3,4‐trienes E are the key intermediates, which then react with another metallocene fragment. The reaction pathways strongly depend on the stability and reactivity of the metallacyclocumulene E , which is influenced by the substituents R, the metallocene fragment, and the employed stoichiometry.…”

Section: Resultsmentioning

confidence: 96%

“…Proposed mechanism for the formation of complex 6. [14] h 1 :h 2 -CCR')MCp' 2 ] were described in the last years (M = Ti, Zr). [16,17] Thereby, Cp' represents substituted or unsubstituted cyclopentadienyl units and the substituents R and R' are alkyl, aryl, SiMe 3 , or SnMe 3 groups.…”

Section: Resultsmentioning

confidence: 99%

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Synthesis and Characterization of Multiferrocenyl‐Substituted Group 4 Metallocene Complexes

Kaleta

Strehler

Hildebrandt

et al. 2012

Chemistry A European J

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The reaction of different metallocene fragments [Cp(2)M] (Cp=η(5)-cyclopentadienyl, M=Ti, Zr) with diferrocenylacetylene and 1,4-diferrocenylbuta-1,3-diyne is described. The titanocene complexes form the highly strained three- and five-membered ring systems [Cp(2)Ti(η(2)-FcC(2)Fc)] (1) and [Cp(2)Ti(η(4)-FcC(4)Fc)](2) (Fc=[Fe(η(5)-C(5)H(4))(η(5)-C(5)H(5))]) by addition of the appropriate alkyne or diyne to Cp(2)Ti. Zirconocene precursors react with diferrocenyl- and ferrocenylphenylacetylene under C-C bond coupling to yield the metallacyclopentadienes [Cp(2)Zr(C(4)Fc(4))](3) and [Cp(2)Zr(C(4)Fc(2)Ph(2))](5), respectively. The exchange of the zirconocene unit in 3 by hydrogen atoms opens the route to the super-crowded ferrocenyl-substituted compound tetraferrocenylbutadiene (4). On the other hand, the reaction of 1,4-diferrocenylbuta-1,3-diyne with zirconocene complexes afforded a cleavage of the central C-C bond, and thus, dinuclear [{Cp(2)Zr(μ-η(1):η(2)-C≡CFc)}(2)] (6) that consists of two zirconocene acetylide groups was formed. Most of the complexes were characterized by single-crystal X-ray crystallography, showing attractive multinuclear molecules. The redox properties of 3, 5, and 6 were studied by cyclic voltammetry. Upon oxidation to 3(n+), 5(n+), and 6(n+) (n=1-3), decomposition occured with in situ formation of new species. The follow-up products from 3 and 5 possess two or four reversible redox events pointing to butadiene-based molecules. However, the dinuclear complex 6 afforded ethynylferrocene under the measurement conditions.

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Dimerization of titanacyclocumulenes to titanium substituted radialenes: synthesis, stability and reactions of five-membered titanacyclocumulenes with a coupling of two 1,4-diphenyl-1,3-butadiyne between two titanocene molecules to radialene-like fused titanacyclopentadiene compounds

Cited by 36 publications

References 30 publications

Examples of Different Reactions of Benzylsulfanyl‐Substituted Alkynes with Selected Complexes of Ti^II and Co^I

Examples of Different Reactions of Benzylsulfanyl‐Substituted Alkynes with Selected Complexes of Ti^II and Co^I

Organic molecules with abnormal geometric parameters

Synthesis and Characterization of Multiferrocenyl‐Substituted Group 4 Metallocene Complexes

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Dimerization of titanacyclocumulenes to titanium substituted radialenes: synthesis, stability and reactions of five-membered titanacyclocumulenes with a coupling of two 1,4-diphenyl-1,3-butadiyne between two titanocene molecules to radialene-like fused titanacyclopentadiene compounds

Cited by 36 publications

References 30 publications

Examples of Different Reactions of Benzylsulfanyl‐Substituted Alkynes with Selected Complexes of TiII and CoI

Examples of Different Reactions of Benzylsulfanyl‐Substituted Alkynes with Selected Complexes of TiII and CoI

Organic molecules with abnormal geometric parameters

Synthesis and Characterization of Multiferrocenyl‐Substituted Group 4 Metallocene Complexes

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Examples of Different Reactions of Benzylsulfanyl‐Substituted Alkynes with Selected Complexes of Ti^II and Co^I

Examples of Different Reactions of Benzylsulfanyl‐Substituted Alkynes with Selected Complexes of Ti^II and Co^I