
Journal of the Chemical Society, Dalton Transactions p. 4533 - 4542 (1996)
Update date:2022-08-05
Topics: Alkynes Structures Intermediates Reactivities Cyclotrimerization
Boorman, P. Michael
Wang, Meiping
Parvez, Masood
The binuclear complexes [Mo2Cl6(tht)3] (both the C2r and Cs isomers, tht = tetrahydrothiophene) have been found to be active catalysts for the selective polymerization and cyclotrimerization of a variety of alkynes. The mononuclear complex [MoCl3(tht)3] shows similar behaviour, leading to the postulate that the active species in all cases is mononuclear. Two unique molybdenum(III) alkyne complexes, [MoCl3(tht)2L] (L = PhC≡CMe or PhC≡CEt) have been isolated and structurally characterized. The structural parameters for these complexes suggest that the alkynes behave as four-electron donors. These complexes are also catalytically active, and the alkyne L is incorporated into the product cyclotrimers and polymers suggesting they are the first intermediates in the formation of active catalysts from the original thioether complexes.
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