The reactivity of the rhenium() allenylidene complex [Re{C C CPh2}(CO)2(triphos)](OTf ) (1) [triphos = MeC(CH2PPh2)3] towards ionic nucleophiles and electrophiles has been explored. Nucleophiles regioselectively attack the Cγ carbon atom leading to the formation of σ-alkynyl complexes, while electrophiles attack the Cβ atom yielding carbyne complexes. The sequential addition of OH and H to 1 at low temperature gave the γ-hydroxyvinylidene complex [Re{CC(H)C(OH)Ph2}(CO)2(triphos)](OTf ) which regenerated 1 above 40 C via H2O elimination.
Backward synthesis of rhenium(I)γ-hydroxyvinylidene and γ-methoxy-vinylidene complexes and their conversion to the allenylidene [Re=C=C=CPh2(CO)2(MeC(CH2Ph2)3](OSO2CF3).
Mantovani, N;Marvelli, L;Rossi, R;Peruzzini, M
2001
Abstract
The reactivity of the rhenium() allenylidene complex [Re{C C CPh2}(CO)2(triphos)](OTf ) (1) [triphos = MeC(CH2PPh2)3] towards ionic nucleophiles and electrophiles has been explored. Nucleophiles regioselectively attack the Cγ carbon atom leading to the formation of σ-alkynyl complexes, while electrophiles attack the Cβ atom yielding carbyne complexes. The sequential addition of OH and H to 1 at low temperature gave the γ-hydroxyvinylidene complex [Re{CC(H)C(OH)Ph2}(CO)2(triphos)](OTf ) which regenerated 1 above 40 C via H2O elimination.File in questo prodotto:
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