Abstract

The synthesis, derivatization and coordination behavior of N-diphenylphosphinomorpholine ( 1) and N-diphenylphosphinopiperazine ( 2) is described. Ligands 1 and 2 react with elemental sulfur or selenium to give the corresponding chalcogenides in good yield. Reaction of 1 with paraformaldehyde leads to the insertion of methylene into P–N bond to give phosphine oxide, Ph 2P(O)CH 2NC 4H 8O in quantitative yield. Treatment of 2 with [Pd(COD)Cl 2] produces both the mononuclear [PdCl 2{(Ph 2PNC 4H 8O)-κP} 2] and the chloro-bridged dinuclear complex, [(OC 4H 8NPh 2P)Pd-(μ-Cl)Cl] 2 whereas the similar reaction of 2 with [Pt(COD)Cl 2] affords only the mononuclear complex [PtCl 2{(Ph 2PNC 4H 8O)-κP} 2]. Interestingly, ligand 2 reacts with Mo(0), W(0), Ru(II), Pd(II), Pt(II) and Au(I) derivatives to furnish exclusively mononuclear complexes. The molecular structures of Ru(II) and Pd(II) dimer have been confirmed by X-ray studies.

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