Formation and Complex Stabilization of a New Chainlike Phosphazene Anion by CoII-Assisted Oxidative Scrambling of [N(PPh2)2]−
✍ Scribed by Prof. Dr. Jochen Ellermann; Dipl.-Chem. Jörg Sutter; Dr. Falk A. Knoch; Dr. Matthias Moll
- Publisher
- John Wiley and Sons
- Year
- 1993
- Tongue
- English
- Weight
- 319 KB
- Volume
- 32
- Category
- Article
- ISSN
- 0044-8249
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✦ Synopsis
The linear phosphazene cation 1[11 has a great synthetic potential and is particularly suitable for the preparation of cyc1ometa11aphosphazenes.~'~ 3l We report now on the formation of the similar phosphazene anion 2 whose sequence of atoms is reversed and its complexation to give a novel spirocyclic cobaltaphosphazene. Surprisingly, when anhydrous cobalt(r1) chloride is treated with lithium bis(dipheny1phosphino)amide (3)t4-61 in the molar ratio 1 :2 in boiling toluene, no complex 4 is formed [Eq. (a)], but in accordance with Equation (b) the red-black spirocyclic cobaltaphosphazene 5['] is obtained with the scrambling of the P-N-P ligand in 3. As shown by the crystal CoCI, + 2 LiN(PPh,), + [Co{N(PPh,),),] + 2 LiCl (4 3 4 Ph, Ph 3COc1, yip;, , F'N ..\ + + Ph,P, , Co, 63LiN(PPh,), N, / p-$ :PPh, + 2 N(PPh,), + 2 Co + 6 LiCI (b) p Ph, 6 Ph, 5 structure analysis (Fig. 1) this spirocycle contains three rings of different sizes, that is, in 5, 2 acts both as a bidentate P ~ [