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- W2087241300 abstract "Abstract Various calix[4]arene and resorc[4]arene ionic compounds substituted by cobalt bis(dicarbollide) anions ( 1 ) have been prepared for the first time. From t Bu‐calix[4]arene ( A ) the complete series of mono‐, di‐, tri‐ and tetrasubstituted derivatives bearing one to four cluster anions on the lower rim ( 3 – 6 ) have been obtained in the form of their alkali‐metal salts by O ‐alkylation with the 1‐dioxane derivative [8‐O(CH 2 CH 2 ) 2 O (+) ‐1,2‐C 2 B 9 H 10 )‐(1',2'‐C 2 B 9 H 11 )‐3,3'‐Co] ( 2 ), all of which are syn or cone isomers. In contrast, disubstitution of the dipropyl ether of t Bu‐calix[4]arene ( B ) led to a mixture of the cone and 1,3‐alternate conformers 7a and 7b , respectively. Starting from tetrapropoxy‐calix[4]arene functionalised at the upper rim by carboxylic acid groups in distal positions ( C ) and an amino‐bridged derivative [8,8'‐μ‐H 2 N<(1,2‐C 2 B 9 H 10 ) 2 ‐3,3'‐Co] ( 8 ), calix[4]arene 9 , disubstituted at the upper rim, was obtained as the main product along with the monosubstituted species 10 . Di‐ and tetrasubstituted ionic products ( 11 – 15 ) were also obtained from resorcarene‐based cavitands by O ‐alkylation with the 1‐dioxane derivative 2 . A pair of regioisomeric disubstitution products, 11a , b , was isolated in the case of the hydroxy cavitand D , while E , functionalised by hydroxymethyl groups on the wide rim, and F , bearing hydroxy groups on the alkylidene bridges, gave the 1,3‐di‐ ( 12 and 14 ) and the tetrasubstituted compounds ( 13 and 15 ), respectively. The molecular structure of the electroneutral dicaesium complex of the dianion 4 was determined by single‐crystal X‐ray diffraction analysis. The two Cs + cations are found in different coordination spheres in the structure of Cs 2 4 . Coordination of the Na + cation by the diethylene glycol chain and one calixarene lower rim oxygen atom was found in the crystal structure of the Na complex of the monoanion 3 . (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)" @default.
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- W2087241300 date "2005-05-01" @default.
- W2087241300 modified "2023-10-05" @default.
- W2087241300 title "Cobalt Bis(dicarbollides)(1-) Covalently Attached to the Calix[4]arene Platform: The First Combination of Organic Bowl-Shaped Matrices and Inorganic Metallaborane Cluster Anions" @default.
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- W2087241300 doi "https://doi.org/10.1002/ejoc.200400811" @default.
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