期刊
ORGANOMETALLICS
卷 40, 期 24, 页码 4143-4149出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.organomet.1c00596
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-
资金
- Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) [387284271-SFB 1349]
The frustrated Lewis pair consisting of an acidic aluminum function and a basic phosphine entity linked by a xanthene spacer can cleave THF. The rate of the ring-opening reaction is 10 times higher for R = C6F5 compared to R = Mes, but computational studies show that aromatic interactions in the secondary coordination sphere do not significantly contribute to lowering the activation barrier.
A frustrated Lewis pair composed of an acidic aluminum function (AlR2) and a basic phosphine entity, linked by a xanthene spacer, is capable of cleaving THF. The rate of the ring-opening reaction is higher by a factor of 10 for R = C6F5 than that for R = Mes. Structural and theoretical investigations revealed for the case of C6F5 aromatic interactions in the secondary coordination sphere which-in case they also exist in the transition state-could aid ring-opening through a preorientation of the reacting functions. However, in detailed computational studies these were found to occur without contributing significantly to the lowering of the activation barrier.
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