ISSN:
0009-2940
Keywords:
Template synthesis
;
Phosphane complexes, macrocyclic, tetradentate
;
Periphery reactions
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Reactions of Coordinated Ligands, XVIII. - Template Syntheses and Periphery Reactions of Macrocyclic Multiphosphane Ligands with Functional GroupsCyclisation of the tridentate phosphanes PhP([CH2]3PRH)2 (R = H, Me) with the divinyl components R′P(CH=CH2)2 [R′ = Ph, NEt2, O(iPr)] 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 [Ni(CN)L]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 · 3 H2O 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).
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19921250802
