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Molybdenum(III) chloride-tetrahydrothiophene (tht) complexes in the catalytic polymerization and cyclotrimerization of alkynes: Structures and reactivities of the possible intermediates [MoCl3(tht)2(PhC≡CR)] (R = Me or Et)

DOI: 10.1039/DT9960004533

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 4533 - 4542 (1996)

Update date:2022-08-05

Topics: Alkynes   Structures   Intermediates   Reactivities   Cyclotrimerization  

Authors:

Boorman, P. MichaelBoorman, P. Michael

Wang, MeipingWang, Meiping

Parvez, MasoodParvez, Masood

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Article abstract of DOI:10.1039/DT9960004533

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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