Cumulene or alkyne? The reduction of a [3]cumulene using Na and K in the presence of 18‐crown‐6 gives the mono‐ and doubly reduced cumulenes as solvent‐separated ion pairs. The analogous reduction with Cs affords a contact‐ion complex. Crystallographic analysis of all the species shows dramatically increased bond‐length alternation upon reduction, while the cumulenic framework remains essentially planar in all cases.
Abstract
The chemical reduction of a [3]cumulene ([3]TrTol) has been explored using alkali metals. Mono‐ and doubly reduced forms of [3]TrTol were isolated as solvent‐separated ion pairs with {Na(18‐crown‐6)THF2}+ and {K(18‐crown‐6)THF2}+ counterions and crystallographically characterized. This allowed analysis of structural parameters of the "naked" anions of [3]TrTol without interference from metal binding. The dianion of [3]TrTol was also isolated as a contact‐ion complex with {Cs(18‐crown‐6)}+ cations, thereby adding the effect of metal coordination to the core. Structural comparisons of anions to the neutral molecule, [3]TrTol, outline monotonic increases in bond‐length alternation (BLA) upon stepwise reduction. The greatest BLA value is found for the contact‐ion complex, which shows an alternating sequence of short and long carbon–carbon bonds, consistent with the structure of an alkyne. In contrast to studies on tetraphenyl[3]cumulene, the cumulenic framework of [3]TrTol remains planar in all the derivatives.
from A via a.sfakia on Inoreader http://bit.ly/2RQKTfo
Δεν υπάρχουν σχόλια:
Δημοσίευση σχολίου
Medicine by Alexandros G. Sfakianakis,Anapafseos 5 Agios Nikolaos 72100 Crete Greece,00302841026182,00306932607174,alsfakia@gmail.com,