Synthesis and characterisation of [AlMen{Si(SiMe3)3}3−n(thf)] (n=1 or 2)

Farwell, James D.; Hitchcock, Peter B.; Läppert, Michael F.

doi:10.1016/j.jorganchem.2007.08.018

Cited by 4 publications

(1 citation statement)

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“…Anhydrous AlCl 3 does not catalyse the polymerization of THF but forms with it a 1:1 complex . Various organoaluminium compounds as well as Ph 2 BCl and B(C 6 F 5 ) 3 also yield complexes with THF. The greatest lengthening of the C−O bonds of THF (by ca.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2017

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The interaction of the titanadihydrofuran metallacycles Cp2Ti[η2‐C(SiMe3)=C(Ph)‐C(Me)2O] (1) and Cp2Ti[η2‐C(SiMe3)= C(Ph)‐CH(Ph)O] (2) with iBu2AlH in n‐hexane at 20°C yields 1 : 1 complexes Cp2Ti[η2‐C(SiMe3)=C(Ph)‐C(Me)2O](iBu2AlH) (4) and Cp2Ti[η2‐C(SiMe3)=C(Ph)‐CH(Ph)O](iBu2AlH) (5) respectively. According to X‐ray diffraction data, the iBu2AlH molecule in 4 is coordinated by its aluminium centre with the oxygen atom whereas the hydride hydrogen atom of the iBu2AlH forms a bridge with the titanium. As a result of the complexation with iBu2AlH, the Ti−O and Ti‐C(SiMe3) bonds of the starting 1 are strongly elongated. An analogous 1 : 1 adduct (11) is formed in the interaction of iBu2AlH with the zirconadihydrofuran derivative Cp2Zr[η2‐C(SiMe3)=C(SiMe3)‐C(Me)2O] (3). Like the Ti−O and Ti‐C(SiMe3) bonds in 1, the Zr−O and Zr‐C(SiMe3) bonds in 3 are considerably elongated as a result of the coordination with iBu2AlH. The reaction of 1 with EtAlCl2 gives a complex, Cp2Ti[η2‐C(SiMe3)=C(Ph)‐C(Me)2O](EtAlCl2) (8), in which the organoaluminium compound is also coordinated by its aluminium centre with the oxygen atom. This leads to a strong elongation of the Ti−O bond. The C−O bond of the metallacycle in 8 is noticeably elongated as well but the Ti‐C(SiMe3) bond length even somewhat shortens. Complexes 4, 5, 8 and 11 are capable of catalysing ring‐opening polymerization of ϵ‐caprolactone. The highest activity is exhibited by complexes 4 and 5.

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Section: Introductionmentioning

confidence: 99%

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

et al. 2017

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Versatile Conversion of N‐Heterocyclic Silylene to Silyl Metal Compounds by Insertion of Divalent Silicon into Metal–Carbon and Metal–Hydrogen Bonds

Xiong

Yao

Drieß

2012

Chemistry A European J

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The facile one-pot reaction of the stable N-heterocyclic silylene LSi: 1 (L=(ArN)C(=CH(2))CH=C(Me)(NAr), Ar=2,6-iPr(2)C(6)H(3)) with Me(2)Zn, Me(3)Al, H(3)Al-NMe(3), and MeLi has been investigated. The silicon(II) atom in 1 is capable of insertion into the corresponding M-C and Al-H bonds under very mild reaction conditions. Thus, Me(2)Zn furnishes the bis(silyl) zinc complex LSi(Me)ZnSi(Me)L 2 as the sole product, irrespective of the molar ratio of the starting materials applied. Moreover, the reactions of 1 with Me(3)Al, H(3)Al-NMe(3), and MeLi lead directly to the 1,1-addition products LSi(Me)(Al(thf)Me(2)) 3, LSi(H)(AlH(2)(NMe(3))) 4, and LSi(Me)Li(thf)(3) 5, respectively. All new compounds 2-5 were fully characterized by multinuclear NMR spectroscopy, mass spectrometry, elemental analyses, and single-crystal X-ray diffraction analyses.

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Oligosilanes

Marschner

2013

Structure and Bonding

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Synthesis and characterisation of [AlMen{Si(SiMe3)3}3−n(thf)] (n=1 or 2)

Cited by 4 publications

References 13 publications

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

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

Versatile Conversion of N‐Heterocyclic Silylene to Silyl Metal Compounds by Insertion of Divalent Silicon into Metal–Carbon and Metal–Hydrogen Bonds

Oligosilanes

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