First structurally characterized five-membered hafnacyclocumulene Cp2Hf(η4-ButC4But)

Burlakov, Vladimir V.; Bogdanov, V. S.; Lyssenko, Konstantin А.; Petrovskii, P. V.; Beweries, Torsten; Arndt, Perdita; Rosenthal, Uwe; Shura, V. B.

doi:10.1007/s11172-008-0171-z

Cited by 12 publications

(13 citation statements)

References 6 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In the cyclo cumulene ring the central double bond is elongated (C21-C22 1.302 (3), C22-C23 1.329(3), C23-C24 1.299(3)) due to the interaction of the in-plane π orbitals of this bond with metal d(π) orbitals. This feature has been described before for the analogous titanium, zirconium, and hafnium complexes [4,5] and was supported by theoretical investigations by Jiao and Jemmis [14].…”

supporting

confidence: 82%

See 1 more Smart Citation

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

Burlakov

Nelyubina

Shur

et al. 2011

Inorganic Chemistry Communications

View full text Add to dashboard Cite

supporting

confidence: 82%

“…1-metallacyclopenta-2,3,4-trienes) [2][3][4]. Additionally the corresponding hafnacyclocumulene complex Cp 2 Hf(η 4 -t-Bu-C 4 -t-Bu) [5] was obtained by reaction of di-n-butylhafnocene with 1,4-bis-tert-butyl-buta-1,3-diyne. Therefore, comparative studies on a series of Cp substituted complexes of the type Cp 2 M(η 4 -t-Bu-C 4 -tBu) (M = Ti, Zr, Hf) (e.g.…”

mentioning

confidence: 99%

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

Burlakov

Nelyubina

Shur

et al. 2011

Inorganic Chemistry Communications

View full text Add to dashboard Cite

“…For the synthesis of the title compound, see: Schock & Marks (1988), and for that of the corresponding unsubstituted cyclopentadienyl complex, see: Burlakov et al (2008). For the use of these complexes as the starting materials for various reactions, see: Burlakov et al (2009).…”

Section: Related Literaturementioning

confidence: 99%

Crystal structure of di-n-butylbis(η⁵-pentamethylcyclopentadienyl)hafnium(IV)

et al. 2015

View full text Add to dashboard Cite

The crystal structure of the title compound, [Hf(C10H15)2(C4H9)2], reveals two independent molecules in the asymmetric unit. The diffraction experiment was performed with a racemically twinned crystal showing a 0.529 (5):0.471 (5) component ratio. Each HfIV atom is coordinated by two pentamethylcyclopentadienyl and two n-butyl ligands in a distorted tetrahedral geometry, with the cyclopentadienyl rings inclined to one another by 45.11 (15) and 45.37 (16)°. In contrast to the isostructural di(n-butyl)bis(η 5-pentamethylcyclopentadienyl)zirconium(IV) complex with a noticeable difference in the Zr–butyl bonding, the Hf—Cbutyl bond lengths differ from each other by no more than 0.039 (3) Å.

show abstract

“…In the last decades, there has been increasing interest in the chemistry of strained metallacycles containing a triple CC bond or cumulated double CC bonds in the ring (see, e.g., refs − ). A remarkable property of these metallacycles is their surprisingly high thermal stability compared with the corresponding purely organic analogues.…”

Section: Introductionmentioning

confidence: 99%

Interaction of the Buchwald Seven-Membered Zirconacyclocumulene Complex with Carbonyl Compounds

et al. 2019

View full text Add to dashboard Cite

The interaction 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) with a 2-fold excess of benzophenone in toluene at 100 °C for 20 h results in the formation of Me 3 SiCC−CCSiMe 3 and a nine-membered dioxazirconacycle Cp 2 Zr[η 2 -OC(Ph) 2 C(SiMe 3 )C 2 C(SiMe 3 )C(Ph) 2 O] (5) containing [3]cumulene group in the ring. Analogous metallacycle (6) is formed on heating of 1 with fluorenone in toluene at 100 °C. A treatment of 5 with HCl in dioxane at 20 °C affords Cp 2 ZrCl 2 and cis-[3]cumulenic diol Ph 2 (HO)C(Me 3 Si)-CC 2 C(SiMe 3 )C(OH)Ph 2 (7) in 85% yield. The reaction of 1 with benzil (PhCO) 2 at 80 °C in benzene proceeds differently than with benzophenone and fluorenone. In this case, a nine-membered dioxazirconacycle Cp 2 Zr[η 2 -Me 3 SiCC(C 2 SiMe 3 )− C(SiMe 3 )C(C 2 SiMe 3 )OC(Ph)C(Ph)O] ( 10) is produced. The nature of products formed in the interaction of 1 with acenaphthenequinone proved to be temperature dependent. Thus, on carrying out the reaction at 20 °C, an 11-membered trioxazirconacycle (11) containing three CC bonds in the ring was isolated from the mixture, whereas at 80 °C the reaction gave a ten-membered tetraoxadizirconacycle (12) and octasubstituted cyclooctatetraene [(Me 3 Si)CC(CCSiMe 3 )] 4 (13). The structures of 5−7 and 10−13 have been determined by X-ray diffraction. The mechanism of the reactions found is discussed.

show abstract

First structurally characterized five-membered hafnacyclocumulene Cp2Hf(η4-ButC4But)

Cited by 12 publications

References 6 publications

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

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

Crystal structure of di-n-butylbis(η⁵-pentamethylcyclopentadienyl)hafnium(IV)

Interaction of the Buchwald Seven-Membered Zirconacyclocumulene Complex with Carbonyl Compounds

Contact Info

Product

Resources

About

First structurally characterized five-membered hafnacyclocumulene Cp2Hf(η4-ButC4But)

Cited by 12 publications

References 6 publications

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

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

Crystal structure of di-n-butylbis(η5-pentamethylcyclopentadienyl)hafnium(IV)

Interaction of the Buchwald Seven-Membered Zirconacyclocumulene Complex with Carbonyl Compounds

Contact Info

Product

Resources

About

Crystal structure of di-n-butylbis(η⁵-pentamethylcyclopentadienyl)hafnium(IV)