DIE CHEMIE DER SCHWEREN CARBEN-ANALOGEN R2M, M=Si, Ge, Sn. X. 7-SILA-NORBORNADIENE: REAKTIONEN MIT HALOGENEN UND THERMOLYSE IN GEGENWART VON METALLORGANISCHEN ODER ORGANISCHEN HALOGENIDEN

Article abstract of DOI:10.1016/0022-328X(86)80389-8

The 7-sila-norbornadienes (I-IV) react rapidly with halogens at -20 to +20 deg C to yield Me2SiHal2 (Hal=Cl, Br, I) and the naphthalene or benzene derivatives (V-VIII).Bromine in CCl4 at 0 deg C, however, caused surprising rearrangement in I giving the 2-bromosilylated naphthalene (IX), since an attack at the alkene group seemed to be preferred.Methylation and methoxylation of IX gave respectively X and XI.Careful hydrolysis of IX yielded the disiloxane XII.Insertions of Me2Si into the Si-Hal, Si-H, Si-C, or Sn-C bonds were not observed at 160-200 deg C, whereas insertions into Sn-Cl or Sn-H bonds occurred smoothly via a one-step mechanism.Halogen is abstracted from different C-Hal bonds leading to Me2SiHal2 and sometimes to Me4Si2Hal2.The degradation of the silylene precursors in these cases is always first order and resembles that of spontaneous thermolysis.