Synthesis and structure of 1,3-bis(hydroxysilyl)-2,4-dimethyl-2,4-diphenylcyclodisilazane

• Published in: Journal of organometallic chemistry Vol. 696; no. 20; pp. 3245 - 3250
• Main Authors: Zheng, Yan, Tan, Yongxia, Dai, Lina, Zhang, Zhijie
• Format: Journal Article
• Language: English
• Published: LAUSANNE Elsevier B.V 01.10.2011; Elsevier
• Subjects: Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; Crystal structure; Cyclodisilazane; Mixed phenyl; Physical Sciences; Science & Technology; Cyclodisilazane; Mixed phenyl; Crystal structure; CYCLODISILAZANES; MOLECULAR-STRUCTURE; CRYSTAL-STRUCTURE; SI-N-BOND; CHEMISTRY
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/j.jorganchem.2011.07.002

Trans-silylation reactions of (Me 3Si) 2NH with PhRSiCl 2 (R = Me, Ph) gave HN(SiMePhCl) 2 ( 1) or ClMePhSiNHSiPh 2Cl ( 2). The treatment of 1,3-dichlorodisilazane ( 1 or 2) with an equimolar amount of n-BuLi led to the formation of 1,3-bis(chloro-silyl)-2,4-dimethyl-2,4-diphenylcyclodisilazane (ClSiMePh) 2(NSiMePh) 2 ( 3) or (ClSiPh 2) 2(NSiMePh) 2 ( 4), which was allowed to hydrolyze to form 1,3-bis(hydroxysilyl)-2,4-dimethyl-2,4-diphenylcyclodisilazane (HOSiMePh) 2(NSiMePh) 2 ( 5) or (HOSiPh 2) 2(NSiMePh) 2 ( 6), respectively. The cyclodisilazane monomers were characterized by elemental analysis, NMR and IR spectroscopy. Compound 3 was obtained as a 4:6 cis/ trans mixture while 4 adopted trans-structure considering the hindrance of pendent groups. In addition, the molecular structures of trans- 5 and trans- 6 were determined by X-ray crystallographic analysis and discussed in detail. 1,3-Bis(chloro-silyl)-2,4-dimethyl-2,4-diphenylcyclodisilazane ( 3, 4) were prepared via a ring-closure reaction of corresponding 1,3-dichlorodisilazane ( 1, 2). The synthesis of these compounds was reported alongside with the structural discussion. A mixture of cis/trans isomers was first observed in the case of 3 while 4 adopted trans-structure. 1,3-Bis(hydroxysilyl)-2,4-dimethyl-2,4-diphenylcyclodisilazane ( 5, 6) were obtained by hydrolysis of cyclodisilazane ( 3, 4). The molecular structures of trans- 5 and trans- 6 were determined by X-ray crystallographic analysis. [Display omitted] ► 1,3-Bis(hydroxysilyl)-2,4-dimethyl-2,4-diphenylcyclodisilazanes were prepared. ► Structures of 5 and 6 were successfully characterized by IR, NMR, EA and X-ray. ► Mixed phenyl substituents on the Si 4N 2 skeleton lead to cis/ trans isomers for 3.