Abstract
Abstract The irradiation of (η5-C5H4R)2Ti(C≡CRc)2 (R = Me, SiMe3 (= TMS); Rc = ruthenocenyl) at the band assignable to CT from Rc to Ti in the presence of equimolar amounts of RcC≡CH and MeO2CC≡CCO2Me smoothly gave titanacyclic complexes (η5-C5H4R)2Ti{–C(Rc)=C(C≡CRc)–CH=C(Rc)–} and (η5-C5H4TMS)2Ti{–C(C≡CRc)=C(Rc)–C(OMe)(C≡CCO2Me)–O–}, respectively, two of which were structurally characterized. The formation of these complexes has been explained by the extremely easy reductive coupling in (η5-C5H4R)2Ti(C≡CRc)2, brought about by photo-excitation at the Rc group, followed by metallacycle formation that involves the resulting diyne unit and the externally added alkynes.
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