Group 1 and mixed Group 1 and 2 metal complexes of dianionic p-tert-butylcalix[4]arenes

Journal article

Group 1 and related complexes of 1,3-O,O′-disubstituted p-tert-butylcalix[4]arene dianions [tBu-calix[4](OR) 2(O)2]2- are reported. Reaction of tBu-calix[4](OMe)2(OH)2 with NaH, K, Rb or Cs gave dimeric [M2{tBu-calix[4](OMe)2-(O) 2}]2 (M = Na 1, K 2, Rb 3 or Cs 4). The X-ray structure of 1 shows that two Na+ ions are exo-bound between the two calix[4]arene ligands while the other two are endo-bound within the calix[4]arene cavities. Reaction of tBu-calix[4](OMe) 2(OH)2 with nBuLi (2 equiv.) gave a mixture of dimeric and monomeric compounds. Complex 1 is cleaved by 15-crown-5 forming [Na2{tBu-calix[4](OMe)2(O) 2}(15-crown-5)]. The complexes 2-4 are cleaved by dibenzo-18-crown-6 forming [M2{tBu-calix[4](OMe)2(O) 2}(dibenzo-18-crown-6)]. Reactions of tBu-calix[4](OR)2-(OH)2 (R = CH2Ph or SiMe3) with Li or Na reagents gave monomeric [M2{ tBu-calix[4](OR)2(O)2}]. The reaction of 1 with CsCl gave [NaCs{tBu-calix[4](OMe)2(O) 2}]2 13 in which the two Cs+ ions are endo-bound. Reaction of 1 with CaCl2 formed [Na2Ca{ tBu-calix[4](OMe)2(O)2}2]. © The Royal Society of Chemistry 2003.

Authors: Dubberley, SR; Blake, A; Mountford, P

• Publication status: Published
• Journal: DALTON TRANSACTIONS
• Issue: 12
• Pages: 2418-2427
• Publication date: 2003-01-01
• DOI: 10.1039/b303725h
• EISSN: 1477-9234
• ISSN: 1477-9226
• Language: English