(Thio)phosphoryl-functionalized enaminoketones: Synthesis, structure, and complexing properties towards transition metal ions

作者：Aleksanyan Diana V^*; Aleksenko Valentina Yu; Nelyubina Yulia V; Klemenkova Zinaida S; Kozlov Vladimir A

来源：Journal of Organometallic Chemistry, 2014, 752: 183-190.

DOI：10.1016/j.jorganchem.2013.12.010

• Enaminoketones
• Tridentate ligands
• Transition metals
• X-ray diffraction

P(X)-functionalized enaminoketones (X = O, S) 1a, b have been readily obtained by the condensation of o-(thio) phosphorylated anilines with sodium salt of benzoylacetaldehyde. The ligands derived exist in solution in the expected ketamino tautomeric form, but, unlike typical enaminoketones, tend to exist as cis-isomers in polar media, favored by the formation of the strong P=O center dot center dot center dot HN intramolecular hydrogen bond. This six-membered hydrogen-bonded ring is also observed in the solid structure of 1a, which, nevertheless, features a trans-configuration of the enaminoketone fragment. Independent from the isomeric composition, the ligands obtained readily form kappa(3)-X,N,O (X = O, S) complexes with a range of transition metal ions (Re(I), Pd(II), Cu(II), and Ni(II)) adopting in all cases the cis-configuration. The structures of the novel compounds are confirmed using multinuclear NMR and IR spectroscopy as well as X-ray crystallography.

• 出版日期2014-2-15