Abstract
A series of new d2 Re (V) alkylidyne complexes were synthesized, including Re(≡CCH2Ph)Cl2(PR3)3 (PR3 = PMe3, and PMePh2), Re(≡CCH2Ph)I2(PMePh2)3, Re(≡CPh)(S2CNEt2)2(PMePh2), [CpRe(≡CPh)(PMePh2)2]Cl, and Re(≡CCH2Ph)(mnt)(PMePh2)2. The complexes Re(≡CCH2Ar)Cl2(PR3)3 (PR3 = PMe3, PMe2Ph, and PMePh2) as well as Re(≡CCH2Ph)I2(PMePh2)3 were found to undergo alkyne metathesis reactions with PhC≡CPh, while the other complexes are inactive. The activity of Re(≡CCH2Ar)Cl2(PR3)3 toward alkyne metathesis reactions with PhC≡CPh is in the order of PMe3 < PMe2Ph < PMePh2. The complex Re(≡CCH2Ph)I2(PMePh2)3 is slightly less reactive than its chloride analog. The difference in the reactivity of the alkylidyne complexes has been studied computationally.
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