Synthesis and characterization of metallatranes with phenyl substituents in atrane cage

• Published in: Inorganica Chimica Acta 2007-02, Vol.360 (2), p.563-578
• Main Authors: Karlov, Sergey S., Selina, Anastasia A., Chernyshova, Eleonora S., Oprunenko, Yuri F., Merkulov, Alexei A., Tafeenko, Victor A., Churakov, Andrei V., Howard, Judith A.K., Zaitseva, Galina S.
• Format: Article
• Language: English
• Subjects: Boratranes; Crystal structure; NMR spectroscopy; Silatranes; Trialkanolamine ligands
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2006.07.109

A series of silatranes and boratranes based on C-phenylsubstituted trialkanolamines has been prepared. Both transalkoxylation and stepwise modification of a preformed metallatrane skeleton were used. The systematic structural study and investigation of chemical behaviour of prepared compounds are presented. A new series of mono- and diphenylsubstituted silatranes and boratranes N(CH 2CH 2O) 2(CHR 3CR 1R 2O)MZ (M = Si, Z = CH 2Cl, C CPh, H, OMenth, R 1, R 2, R 3 = H, Ph; M = B, Z = nothing, R 1, R 2, R 3 = H, Ph) have been synthesized. Both transalkoxylation and stepwise modification of a preformed metallatrane skeleton were used. The chloromethyl derivatives N(CH 2CH 2O) 2(CHRCHRO)SiCH 2Cl (R = H, Ph) react with tert-BuOK under intramolecular cycle expansion to give 1- tert-butoxy-2-carba-3-oxahomosilatranes N(CH 2CH 2O)(CH 2CH 2OCH 2)(CHRCHRO)SiO t Bu (R = H, Ph). The treatment of boratranes N(CH 2CH 2O) 2(CH 2CR 1R 2O)B (R 1,R 2 = H, Ph) with triflic acid and trimethylsilyl triflate results in the products of electrophilic attack at the nitrogen atom. The molecular structures of four silatranes and one boratrane bearing phenyl groups in the atrane skeleton were determined by the X-ray structure analysis.