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, Nicoletta;MARVELLI, Lorenza;ROSSI, Roberto;
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:
Non ci sono file associati a questo prodotto.
I documenti in SFERA sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
