Confinement of [(H2O)2∩([18]Crown-6)] in a Disc-Shaped Cavity Lined with Six Nickel(II) Macrocycle Dimers Acting as Divergent Receptor Molecules
✍ Scribed by Colin L. Raston; Peter J. Nichols; Krisztian Baranyai
- Publisher
- John Wiley and Sons
- Year
- 2000
- Tongue
- English
- Weight
- 295 KB
- Volume
- 39
- Category
- Article
- ISSN
- 0044-8249
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✦ Synopsis
The nickel(ii) complex [Ni(tmtaa)] (Equation (1)) and its analogue with two methyl groups on each of the phenyl rings of the ligand, [Ni(omtaa)], are versatile receptors for a range of globular molecules. [1±4] A 1:1 complex between [Ni(tmtaa)] and fullerene is known, in which the macrocycle acts as a divergent receptor for C 60 . A fullerene perches in each macrocycle cavity in an infinite zigzag array. [1] A similar structure is found for C 70 with [Ni(omtaa)]. [3] For smaller globular molecules, including 1,2-dicarba-closo-dodecaborane(12), tetraphosphorus trisulfide, tetraphosphorus triselenide, and cyclo-octasulfur, the [Ni(tmtaa)] complex self associates through aromatic faces into dimers and these dimers then act as divergent homotopic receptors with a 1:2 ratio of guest:host were observed; 31 P{ 1 H} NMR (C 6 D 6 , 85% H 3 PO 4 external): d À 319.4 (K 2 PR*). The reaction of KR* and PCl 3 in the molar ratio 2:1 gave quantitative amounts of R*ClPÀPClR* (d( 31 P) 188). [2] 3 d: A solution of 1 b (0.199 g, 0.500 mmol) in THF (2 mL) was added to CuI (0.160 g, 0.840 mmol), and after 1 h the insoluble components were removed by centrifugation. Hexameric dicopper supersilylphosphanediide (3 d) crystallized in the form of yellow-green prisms (yield ca. 50 %) from the remaining solution in the course of five days. The compound 3 d, which was insoluble in organic media, was characterized by X-ray structure analysis (Figure 5).