142320-52-3Relevant academic research and scientific papers
Reactions of Coordinated Ligands, XVIII. - Template Syntheses and Periphery Reactions of Macrocyclic Multiphosphane Ligands with Functional Groups
Brauer, David J.,Doerrenbach, Frank,Lebbe, Thomas,Stelzer, Othmar
, p. 1785 - 1794 (2007/10/02)
Cyclisation of the tridentate phosphanes PhP(3PRH)2 (R=H, Me) with the divinyl components R'P(CH=CH2)2 within Ni(II) templates affords complexes NiBr2L (3a-f) of functionalised macrocyclic tetraphosphanes (L) in almost quantitative yields.An X-ray structural analysis of the cyano complex PF6 (5a), obtained by metathetical reactions, reveals a folded 14-membered macrocyclic Ligand L.The P atoms occupy axial and equatorial positions within the trigonal-bipyramidal ligand arrangement with an equatorial CN group.By periphery reactions at the P-NEt2 function of the 14-membered ring system P-OH, P-O-, P-Cl, P-OR''derivatives (R''=Me, iPr, CH2CH=CH2) are formed.Addition of methyl acrylate to the P-H functions in 3d and 3f leads to macrocyclic diesters 12a, 12b.By cleavage of the P-N bond in 3a with concentrated aqueous HBr a complex of composition 7a*HBr*3H2O is obtained.An X-ray structural analysis of the latter shows a P-OH functionalised macrocyclic tetraphosphane occupying the four basal positions within a square pyramidal coordination geometry at Ni(II). Key Words: Template synthesis / Phosphane complexes, macrocyclic, tetradentate / Periphery reactions
