Reactions of Coordinated Ligands. Part 19: Template Synthesis of a Macrocyclic Secondary Tetraphosphine by Oxidative Demetallation of Crown Phosphine Ni(II) Complexes
✍ Scribed by Thomas Lebbe; Peter Machnitzki; Othmar Stelzer; William S. Sheldrick
- Publisher
- Elsevier Science
- Year
- 2000
- Tongue
- French
- Weight
- 263 KB
- Volume
- 56
- Category
- Article
- ISSN
- 0040-4020
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✦ Synopsis
The nickel(II) complex 3 containing a 14-membered macrocyclic triphosphine phosphinate ligand is obtained by regioselective oxidation of the crown phosphine nickel(II) complex 2c with molecular oxygen. The X-ray structure of 3•H 2 O (space group P2 1 /c) has been determined. Oxidation of the macrocyclic phosphinous acid nickel(II) complex 2a (P 4 donor set) with H 2 O 2 /HCl or Br 2 and subsequent demetallation affords the macrocyclic phosphinic acid 5. Reaction of its methylester 6 with thionyl chloride and subsequent reduction with LiAlH 4 gives the novel macrocyclic PH functional tetradentate phosphine 8 in high yields.