4526-07-2Relevant articles and documents
Interaction of the buchwald seven-membered zirconacyclocumulene complex with carbonyl compounds
Burlakov, Vladimir V.,Andreev, Maxim V.,Bogdanov, Vyacheslav S.,Smol'Yakov, Alexander F.,Minacheva, Mariya Kh.,Shur, Vladimir B.
, p. 2636 - 2646 (2019)
The interaction of the Buchwald seven-membered zirconacyclocumulene Cp2Zr[4-Me3SiC4(SiMe3)-C(C2SiMe3)=CSiMe3] (1) with a 2-fold excess of benzophenone in toluene at 100 °C for 20 h results in the formation of Me3SiCC-CCSiMe3 and a nine-membered dioxazirconacycle Cp2Zr[2-OC(Ph)2C(SiMe3)C2C(SiMe3)C(Ph)2O] (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 Cp2ZrCl2 and cis-[3]cumulenic diol Ph2(HO)C(Me3Si)CC2C(SiMe3)C(OH)Ph2 (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 Cp2Zr[2-Me3SiCaC(C2SiMe3)-C(SiMe3) C(C2SiMe3)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 CaC bonds in the ring was isolated from the mixture, whereas at 80 °C the reaction gave a ten-membered tetraoxadizirconacycle (12) and octasubstituted cyclooctatetraene [(Me3Si)CaC(CCSiMe3)]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.
Tuning of cross-Glaser products mediated by substrate-catalyst polymeric backbone interactions
Ali, Md. Ehesan,Dar, Arif Hassan,Gowri, Vijayendran,Jayamurugan, Govindasamy,Kaur, Sharanjeet,Mukhopadhyaya, Aritra,Neethu, K. M.,Sartaliya, Shaifali,Selim, Abdul
supporting information, p. 2582 - 2585 (2020/03/10)
Tuning of cross-Glaser products using different polymeric backbones supported by copper oxide nano-catalysts has been demonstrated by tweaking the substrate-catalyst interactions under greener conditions. Further, highly reactive magnetically separable and recyclable catalyst with scalability is demonstrated.
Halogen bonding of (iodoethynyl)benzene derivatives in solution
Dumele, Oliver,Wu, Dino,Trapp, Nils,Goroff, Nancy,Diederich, Francois
supporting information, p. 4722 - 4725 (2015/04/27)
Halogen bonding (XB) between (iodoethynyl)benzene donors and quinuclidine in benzene affords binding free enthalpies (δG, 298 K) between -1.1 and -2.4 kcal mol-1, with a strong LFER with the Hammett parameter σpara. The enthalpic dri