Abstract
The photochemical decomposition of 7-sila- and 7-germa-norbornadienes ( Ia, b) was studied by the CIDNP 1H technique. The reactions proceeds by a two-step mechanism via the reversible formation of singlet biradicals, II. The triplet biradical ( II), formed as a result of S-T conversion of ( II)(S), irreversibly decomposes giving Me 2E (E = Si, Ge). The insertion of Me 2E into the CBr bond of PhCH 2Br and the SnCl bond of Me 3SnCl occurs via a radical mechanism, as deduced from the CIDNP effects observed in these reactions.
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