Equilibrium between metallaindans and aryne olefin-metal complexes

Palladium-Catalyzed Cycloaddition Reactions of Arynes

“…The early work of Erker [16,17] and later extensive studies by Buchwald [5,8] have shown that the aryne-zirconium complex 17 is susceptible to insertion of a variety of unsaturated species to give the corresponding zirconacycles (Scheme 3). The insertion of substituted olefins such as stilbene is stereospecific, since trans-stilbene reacts with 17 to afford metallacycle 18, while cis-stilbene affords 19 [17].…”

Investigations on 1‐Metallaindanes

“…[17] It has been shown that the reaction of 11, the 2-zircona analogue of 2, with B(C 6 F 5 ) 3 furnished the intramolecular ion pair 12 (Scheme 6). [5] It was therefore of interest to investigate the reaction of 2 with B(C 6 F 5 ) 3 in order to generate the zwitterionic complex 13.…”

“…The known complex 2 [17] was obtained from the reaction of 1 with Cp 2 ZrCl 2 . To a mixture of 2 (53.4 mg, 0.16 mmol) and B(C 6 F 5 ) 3 (84.0 mg, 0.16 mmol), 1 mL of C 6 H 5 Br was added at Ϫ30°C.…”

Etudes sur les composés organométalliques. Partie XXI. Contribution à l'étude de la décomposition du tétracyclohexyltitane

“…Cette reaction conduit soit a des espkces phknyltitane ou benzynetitane comme l'indique la presence de chlorobenzhe et d'o -dichlorobenzkne lors de la chlorolyse. La formation de benzyne est observke dans le cas du diphtnyltitanockne [7] et du diphtnylzirconockne [8].…”