Ambiguous reactivity of Li/Cl phosphinidenoid complexes under redox conditions - a novel dichotomy in phosphorus chemistry

作者：Garcia Cristina Murcia; Bauza Antonio; Schnakenburg Gregor; Frontera Antonio^*; Streubel Rainer^*

来源：Chemical communications, 2017, 53(5): 933-936.

DOI：10.1039/c6cc09620d

A novel ambiguous reactivity of Li/Cl phosphinidenoid complexes under redox conditions is described. The outcome of the reaction with hexafluoroacetone is highly dependent on the P-substituent as fluoride substitution occurred in the case of R = CPh3 and C5Me5 via a radical pathway, whereas for R = CH(SiMe3)(2) a complex having a novel 1,2-diol-type P-ligand was obtained via a closed-shell pathway. DFT calculations reveal a new SET pathway starting with a noncovalent pi-hole complex between the phosphinidenoid anion and hexafluoroacetone followed by an elimination of LiF. The second, closed-shell reaction course is strongly influenced by a noncovalent O center dot center dot center dot Si interaction established after the initial nucleophilic attack.

• 出版日期2017