The azaphosphiridine to terminal phosphinidene complex rearrangement - looking for non-covalent interactions of a highly reactive species

作者：Franco Jose Manuel Villalba; Espinosa Ferao Arturo; Schnakenburg Gregor; Streubel Rainer

来源：Chemical Communications, 2013, 49(83): 9648-9650.

DOI：10.1039/c3cc45477k

Azaphosphiridine complexes 4a,a%26apos;, intermediates in the reaction of P-C5Me5 substituted Li-Cl phosphinidenoid complex 2 and C-furyl carbaldimine 3, rearranged selectively to give the novel N,P,C-cage complex 5a. Transient terminal phosphinidene complex 7a was trapped with phenyl acetylene (8) forming the new N,P,C-cage complex 9. DFT calculations provide evidence for a thermally allowed aza-phospha-Cope rearrangement that led to the P-amino substituted phosphinidene complex 7a, which is stabilized by non-covalent interactions in addition to typical through-bond electronic effects.

• 出版日期2013