2002/01/18 by Oliver Minge, Norbert W. Mitzel, Hubert Schmidbaur · 1 citation
Chemistry · #Synthesis and characterization of novel inorganic/organometallic compounds #Organoboron and organosilicon chemistry #Coordination Chemistry and Organometallics
paper · doi:10.1021/om0108595
openalex publication_date 2002/01/18 · openalex created_date 2025/10/10 · openalex updated_date 2026/06/26
The use of tri(alkoxy)silanes (RO) 3 SiH, which have recently become commercially available in greater than research scale quantities (R = Me, Et), has been probed for the preparation of hydrogen-rich arylsilanes ArSiH 3 . It was found that the silylation of aryl-lithium or (in situ) aryl-Grignard reagents is followed by RO/H ligand redistribution and can lead to fully hydrogenated products in a one-pot reaction without employment of any additional metal hydride. After hydrolytic workup, the overall yields are between 20 and 30%. Silane gas and tetra(alkoxy)silanes are the main byproducts. At an early stage of the reactions, the whole set of mixed-ligand silanes (RO) 3 - n H n SiAr can be detected by GLC/MS techniques. Induced by the organometallic base, the reaction also includes aryl scrambling to give silanes Ar n SiH 4 - n, Ar n Si(OR) 4 - n, and Ar n Si(H/OR) 4 - n . A reaction scheme is proposed that accounts for the product distribution. Examples are given for Ar = phenyl, 4-biphenylyl, 4,4‘-biphenyldiyl, 1-naphthyl, and 2-anisyl. The reaction gives only very poor yields of di(silyl)arenes. Silanes of this type were therefore prepared from (RO) 3 SiH compounds and the corresponding di(halo)arenes by the in situ Grignard procedure followed by LiAlH 4 reduction. Representative cases are 1,2- and 1,4-di(silyl)benzene and 1,4-di(silyl)-2,5-dimethylbenzene. The primary reaction products 1,4-(EtO) 3 SiC 6 H 4 Si(OEt) 3 and 1,4-[(EtO) 3 Si] 2 -2,5-(CH 3 ) 2 C 6 H 2 have been isolated, and the crystal structure of the latter was determined.