Reaktionen koordinierter Liganden, XVIII. Templatsynthesen und Peripheriereaktionen makrocyclischer Multiphosphanliganden mit funktionellen Gruppen

Reactions of Coordinated Ligands, XVIII. – Template Syntheses and Periphery Reactions of Macrocyclic Multiphosphane Ligands with Functional Groups Cyclisation of the tridentate phosphanes PhP([CH 2 ] 3 PRH) 2 (R = H, Me) with the divinyl components R′P(CHCH 2 ) 2 [R′ = Ph, NEt 2 , O( i Pr)] within Ni(II) templates affords complexes NiBr 2 L ( 3a–f ) of functionalised macrocyclic tetraphosphanes (L) in almost quantitative yields. An X‐ray structural analysis of the cyano complex [Ni(CN)L]PF 6 ( 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–NEt 2 function of the 14‐membered ring system POH, PO − , PCl, POR″ derivatives (R″ = Me, i Pr, CH 2 CHCH 2 ) are formed. Addition of methyl acrylate to the PH functions in 3d and 3f leads to macrocyclic diesters 12a, 12b . By cleavage of the PN bond in 3a with concentrated aqueous HBr a complex of composition 7a · HBr · 3 H 2 O is obtained. An X‐ray structural analysis of the latter shows a POH functionalised macrocyclic tetraphosphane occupying the four basal positions within a square pyramidal coordination geometry at Ni(II).