433217-83-5Relevant academic research and scientific papers
Syntheses and crystal structures of P-transition-metalated iminophosphoranes, Cp*(CO)2M{P(NPh)(OMe)2} (M = Fe and Ru)
Kubo, Kazuyuki,Nakazawa, Hiroshi,Inagaki, Hiroyasu,Miyoshi, Katsuhiko
, p. 1942 - 1948 (2002)
The reaction of[Cp*(CO)2Fe{P(NHPh)(OMe)2}]PF6 with NaNH2 yielded the P-iron-bonded iminophosphorane Cp*(CO)2Fe{P(NPh)(OMe)2}, with deprotonation from the NHPh group on the phosphorus. The ruthenium analogue, Cp*(CO)2Ru{P(NPh(OMe)2}, was also prepared in a similar manner. The spectroscopic properties of the metallaiminophosphoranes are quite similar to those of their P=O analogue, i.e., phosphonate complexes. The X-ray structure analyses revealed that the P-N bond in Cp*(CO)2Fe{P(NPh)(OMe)2} is comparable in length to that of the ruthenium analogue, Cp*(CO)2Ru{P(NPh)(OMe)2}, and both are considerably shorter than a P-N single bond. These observations strongly suggest that the P-N bonds in the P-metalated iminophosphoranes have substantial double-bond character. The structural features of the metallaiminophosphorane of iron resemble those of the starting cation complex, indicating that their electronic structures are basically similar. The iron-iminophosphorane is thermally stable compared with its Cp analogue, which is not stable enough to isolate, suggesting that both steric and electronic factors are responsible for the stability of the Cp* complexes.
