Hydroxyalkyl Complexes and Hemiaminal Formation in the Reaction of o-Diphenylphosphinobenzaldehyde with Rhodium(I) Dihydrazone Complexes

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• 作者：Rachad El Mail ; Marí ; a A. Garralda ; Ricardo Herná ; ndez ; Lourdes Ibarlucea ; Elena Pinilla ; and M. Rosario Torres
• 刊名：Organometallics
• 出版年：2000
• 出版时间：December 11, 2000
• 年：2000
• 卷：19
• 期：25
• 页码：5310 - 5317
• 全文大小：105K
• 年卷期：v.19,no.25(December 11, 2000)
• ISSN：1520-6041

文摘

The diimino complex Rh(COD)(bdh)Cl (bdh: H₂NN=C(Me)C(Me)=NNH₂) reacts witho-diphenylphosphino(benzaldehyde) (PCHO) in the presence of PPh₃ to give acylhydrido[Rh(H)(PCO)(PPh₃)(bdh)]⁺ species. When using Rh/PCHO = 1:2 stoichiometric ratios,oxidative addition of one PCHO and P-coordination of another PCHO occurs. The aldehydegroup then undergoes two competitive reactions: (i) addition of one free amino group togive a stable hemiaminal and a complex [Rh(H)(PCO)(Pbdh)]⁺ that contains a new PNNligand coordinated via the imino nitrogens and the phosphorus atom or (ii) insertion intoRh-H to give the hydroxyalkyl complex [Rh(PCO)(PCHOH)(bdh)]⁺. The complexes havebeen fully characterized, and X-ray diffraction structures of both of them are reported. Someintermediates in the competitive reactions have been spectroscopically characterized, andthe transformation of the hemiaminal group into imine to give a PaNN ligand in the complex[Rh(H)(PCO)(Pabdh)]⁺ has also been studied.