Complexation of Titana‐ and Zirconadihydrofuran Metallacycles with Organoaluminium Compounds and Catalytic Activity of the Resulting Complexes in Polymerization of ϵ‐Caprolactone

Burlakov, Vladimir V.; Bogdanov, V. S.; Sokolova, Olga O.; Arndt, Perdita; Spannenberg, Anke; Minacheva, M. Kh.; Anan'ev, Iwan A.; Rosenthal, Uwe; Shur, V. B.

doi:10.1002/slct.201601732

Cited by 2 publications

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“…Recently, we found that the reaction of a zirconadihydrofuran with HAl(i-Bu) 2 gave a 1:1 complex where, in addition to the coordination of the aluminium atom to the oxygen of the intact furan ring, a Zr-H-Al bridge was obtained. This compound also behaves as an active catalyst in the ROP of "-caprolactone (Burlakov et al, 2017). In addition, a zwitterionic hafnocene furanone-B(C 6 F 5 ) 3 adduct has been synthesized and structurally characterized (Beweries et al, 2009).…”

Section: Chemical Contextmentioning

confidence: 99%

Synthesis and crystallographic characterization of [2,2-bis(η⁵-pentamethylcyclopentadienyl)-3,4-bis(trimethylsilyl)-2-zirconafuran-5-one-κO⁵]triisobutylaluminium

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The crystal structure of the title zwitterionic zirconocene complex containing a furanone unit, [AlZr(C 10 H 15 ) 2 (C 4 H 9 ) 3 (C 9 H 18 O 2 Si 2 )], is reported. On reacting a zirconafuranone with two equivalents of HAl(i-Bu) 2 , disproportionation of the Lewis acid results in the formation of a triisobutylaluminium fragment, Al(i-Bu) 3 , which coordinates to the exocyclic carbonyl O atom of the zirconafuranone ring. Single-crystal X-ray diffraction reveals that the zirconafuranone ring remains intact with coordination of the aluminium to the exocyclic O atom. One of the i-butyl groups is disordered over two sets of sites, with an occupancy ratio of 0.731 (3):0.269 (3).

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Section: Chemical Contextmentioning

confidence: 99%

Synthesis and crystallographic characterization of [2,2-bis(η⁵-pentamethylcyclopentadienyl)-3,4-bis(trimethylsilyl)-2-zirconafuran-5-one-κO⁵]triisobutylaluminium

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Controlled Polymerization of ϵ‐Caprolactone using Aluminum and Zinc Complexes with Iminophosphorane Ligands

Zhang

Wang

2020

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Several novel aluminum complexes [Al(R1)2{o‐O C(R)=C(H)P(Ph2)=N)C6H4(3,5‐Me2 ‐pyrazolyl)} (R=Ph, R1=Me, 3; R=Ph, R1=Et, 4; R=tBu, R1=Me, 5) had been prepared. These aluminum complexes were structurally characterized by nuclear magnetic resonance spectroscopy (1H, 13C and 31P) and elemental analyses. The aluminum complex 3 was determined by X‐ray diffraction. The catalytic activities of the aluminum complexes towards the ring‐opening polymerization (ROP) of ϵ‐caprolactone (ϵ‐CL) were investigated. Catalysis of two known zinc complexes with the same ligands, [Zn(Et) {o‐(OC(R)=C(H)P(Ph2)=N)C6H4(3,5‐Me2‐pyrazolyl)}] (R=Ph, 6; R=tBu, 7), in the ROP of ϵ‐CL was also determined. The catalytic results show that these complexes are effective catalysts in the ROP of ϵ‐CL. Kinetics of the polymerization was studied. These polymerizations reaction are consistent with the first‐order kinetic equation. The molecular weight of the polycaprolactone (PCL) is linear with the monomer conversion, and the molecular weight distribution is narrow. These kinetic studies confirm that the catalytic process is controllable.

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Complexation of Titana‐ and Zirconadihydrofuran Metallacycles with Organoaluminium Compounds and Catalytic Activity of the Resulting Complexes in Polymerization of ϵ‐Caprolactone

Cited by 2 publications

References 31 publications

Synthesis and crystallographic characterization of [2,2-bis(η⁵-pentamethylcyclopentadienyl)-3,4-bis(trimethylsilyl)-2-zirconafuran-5-one-κO⁵]triisobutylaluminium

Synthesis and crystallographic characterization of [2,2-bis(η⁵-pentamethylcyclopentadienyl)-3,4-bis(trimethylsilyl)-2-zirconafuran-5-one-κO⁵]triisobutylaluminium

Controlled Polymerization of ϵ‐Caprolactone using Aluminum and Zinc Complexes with Iminophosphorane Ligands

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Complexation of Titana‐ and Zirconadihydrofuran Metallacycles with Organoaluminium Compounds and Catalytic Activity of the Resulting Complexes in Polymerization of ϵ‐Caprolactone

Cited by 2 publications

References 31 publications

Synthesis and crystallographic characterization of [2,2-bis(η5-pentamethylcyclopentadienyl)-3,4-bis(trimethylsilyl)-2-zirconafuran-5-one-κO5]triisobutylaluminium

Synthesis and crystallographic characterization of [2,2-bis(η5-pentamethylcyclopentadienyl)-3,4-bis(trimethylsilyl)-2-zirconafuran-5-one-κO5]triisobutylaluminium

Controlled Polymerization of ϵ‐Caprolactone using Aluminum and Zinc Complexes with Iminophosphorane Ligands

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Synthesis and crystallographic characterization of [2,2-bis(η⁵-pentamethylcyclopentadienyl)-3,4-bis(trimethylsilyl)-2-zirconafuran-5-one-κO⁵]triisobutylaluminium

Synthesis and crystallographic characterization of [2,2-bis(η⁵-pentamethylcyclopentadienyl)-3,4-bis(trimethylsilyl)-2-zirconafuran-5-one-κO⁵]triisobutylaluminium