Unprecedented isolation of alk-1-en-3-yn-1-yl intermediates in the catalytic oligomerisation of alk-1-ynes by cationic Lewis base-free zirconocene complexes

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Abstract
[Zr(C5Me5)2Me{(4-C6H4F)4}]1 catalyses the rapid regioselective oligomerisation of RCCH to 2,4-disubstituted-but-1-en-3-ynes (R = But, Prn, Me, Ph, 4-C6H4Me) and 1,4,6-trisubstituted-hexa-1,3-dien-5-ynes (R = Prn, Me); isolation of the unprecedented crystalline complexes, [Zr(C5Me6)2{CHC(R)CCR}]+(R = But2a, Prn2b) and [Zr(C5Me5)2{C(SiMe3)CHCHC(SiMe3)CCSiMe3}]+3f, provides firm evidence for the catalytic cycle.