Synthesis and crystal structure of the first five-membered ansa-metallacyclocumulene rac-(ebthi)Zr(η4-t-Bu-C4-t-Bu)

Burlakov, Vladimir V.; Nelyubina, Yulia V.; Shur, V. B.; Arndt, Perdita; Kaleta, Katharina; Baumann, Wolfgang; Rosenthal, Uwe

doi:10.1016/j.inoche.2011.03.046

Cited by 5 publications

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“…As an extension of early investigations by reaction of rac ‐(ebthi)Zr(η 2 ‐btmsa) with t Bu‐C≡C‐C≡C‐ t Bu the first five‐membered ansa ‐metallacyclocumulene rac ‐(ebthi)Zr(η 4 ‐ t Bu‐C 4 ‐ t ‐Bu) was obtained . In the reaction of Cp 2 Ti(η 2 ‐btmsa) with bis(ferrocenyl)acetylene Fc‐C≡C‐Fc after substitution of the bis(trimethylsilyl)acetylene a titanacyclopropene and with the 1,3‐diyne Fc‐C≡C‐C≡C‐Fc a titanacyclocumulene was isolated.…”

Section: Products Of Reactions With Diynesmentioning

confidence: 99%

Recent Synthetic and Catalytic Applications of Group 4 Metallocene Bis(trimethylsilyl)acetylene Complexes

Rosenthal

2019

Eur J Inorg Chem

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With the 30 years old first example of a stable group 4 metallocene bis(trimethylsilyl)acetylene (btmsa) complex Cp2Ti(η2‐btmsa) a series of similar complexes like Cp′2M(η2‐btmsa) (M = Ti, Zr; Cp′ = Cp, Cp* as η5‐pentamethylcyclopentadienyl and Cp′2 = rac‐(ebthi) as rac‐1,2‐ethylene‐1,1′‐bis(η5‐tetrahydroindenyl) ) represent excellent sources for the generation of the very reactive coordinatively and electronically unsaturated complex fragments [Cp'2M], which were used in many synthetic and catalytic reactions. Examples for this were oresented in several papers and summarized in some reviews. In this update new reactions of group 4 metallocene bis(trimethylsilyl)acetylene complexes towards symmetrically and unsymmetrically α‐dihetero‐substituted alkynes, reactions with other alkynes, di‐ and polyynes to metallacyclopentadienes as well as the conversions of the formed products are summarized. Additionally, novel synthetic applications of the formed metallacyclopentadienes on the basis of the zirconocene bis(trimethylsilyl)acetylene complex Cp2Zr(py)(η2‐btmsa) are highlighted. Reactions with imines, neutral N‐donor ligands, E‐H compounds (E = N, O, P), molecular hydrogen, water, phosphino‐ and aminoboranes, E‐Cl compounds (E = C, P), disilylated germylenes and aryloxy ketones were described. Different self‐assembly reactions to multinuclear complexes by using group 4 metallocene bis(trimethylsilyl)acetylene complexes in C‐C coupling reactions with or without C‐H bond activation to tri‐ or tetranuclear complexes are considered, too. These examples are discussed following the general L‐M‐S principle for stoichiometric and catalytic reactions, whereby different ligands L (L = Cp′ = Cp, Cp*, rac‐ebthi), metals M (M = Ti, Zr, Hf) and substrate substituents S influence the reactivity and the obtained products.

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Section: Products Of Reactions With Diynesmentioning

confidence: 99%

Recent Synthetic and Catalytic Applications of Group 4 Metallocene Bis(trimethylsilyl)acetylene Complexes

Rosenthal

2019

Eur J Inorg Chem

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“…This remarkable feature of seven-membered zirconacyclocumulenes, differing them from their unstable purely organic cyclic analogues (see, for example, ref ), can be due to the coordination of the central CC double bond of the butatrienyl fragment with the zirconium atom. An analogous interaction of the butatrienyl CC bond with the metal is apparently the reason for an abnormally high stability of the corresponding five-membered titana-, zircona-, and hafnacyclocumulenes, ,− representing the smallest cyclic [3]cumulenes known up to now.…”

Section: Introductionmentioning

confidence: 99%

Thermal Isomerization of the Buchwald Seven-Membered Zirconacyclocumulene and Its Interaction with Acetylenes. Synthesis and Structures of Novel Seven-Membered Zirconacyclocumulene Complexes

et al. 2015

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On prolonged heating of the Buchwald seven-membered zirconacyclocumulene Cp 2 Zr[η 4 -Me 3 SiC 4 (SiMe 3 )− C(C 2 SiMe 3 )CSiMe 3 ] (1) in toluene at 100 °C, the isomerization of 1 takes place with the formation of a seven-membered zirconacyclocumulene complex, Cp 2 Zr[η 4 -Me 3 SiC 4 (SiMe 3 )−C(SiMe 3 )C(C 2 SiMe 3 )] (8), containing the Me 3 SiCC group in α-position and the SiMe 3 group in β-position with respect to the Zr atom. A remarkable peculiarity of complex 8 is its ability to undergo a rapid degenerate rearrangement at room temperature in toluene solution, as a result of which only two rather than four singlets of the Me 3 Si groups are observed in the 1 H NMR spectrum of 8 under such conditions. At temperatures below 200 K, the rate of this rearrangement decreases and, as a consequence, the 1 H NMR spectrum of 8 acquires the normal view. If 1 is heated at 100 °C in the presence of acetylenes such as 1,4-bis(tert-butyl)butadiyne ( t BuCC−CC t Bu) and tolane, the corresponding seven-membered zirconacyclocumulenes, viz., Cp 2 Zr[η 4 -t BuC 4 ( t Bu)−C(C 2 SiMe 3 )CSiMe 3 ] ( 7) and Cp 2 Zr[η 4 -Me 3 SiC 4 (SiMe 3 )−C(Ph)CPh] (14), are formed along with free Me 3 SiCC−CCSiMe 3 . The interaction of 1 with 1,4diphenylbutadiyne (PhCC−CCPh) at 100 °C leads to the formation of a mixture of products, from which a zirconacyclopentadiene metallacycle, Cp 2 Zr[η 2 -PhCC(C 2 Ph)−C(C 2 Ph)CPh] (10), as well as seven-membered zirconacyclocumulenes Cp 2 Zr[η 4 -PhC 4 (Ph)−C(C 2 SiMe 3 )CSiMe 3 ] (11), Cp 2 Zr[η 4 -Me 3 SiC 4 (SiMe 3 )−C(C 2 Ph)CPh] (12), and Cp 2 Zr[η 4 -PhC 4 (Ph)−C(C 2 Ph)CPh] (13) were isolated. The structures of 8, 9, 10, 12, and 14 have been established by X-ray crystallography. The mechanism of the reactions found is discussed.

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Five-Membered Rings With Other Elements

Sadimenko

2022

Comprehensive Heterocyclic Chemistry IV

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Synthesis and crystal structure of the first five-membered ansa-metallacyclocumulene rac-(ebthi)Zr(η4-t-Bu-C4-t-Bu)

Cited by 5 publications

References 17 publications

Recent Synthetic and Catalytic Applications of Group 4 Metallocene Bis(trimethylsilyl)acetylene Complexes

Recent Synthetic and Catalytic Applications of Group 4 Metallocene Bis(trimethylsilyl)acetylene Complexes

Thermal Isomerization of the Buchwald Seven-Membered Zirconacyclocumulene and Its Interaction with Acetylenes. Synthesis and Structures of Novel Seven-Membered Zirconacyclocumulene Complexes

Five-Membered Rings With Other Elements

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