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• W2037442270 abstract "The reactions of either p-tert-butylcalix[4]areneH4 [Cax(OH)4], 1,3-dimethoxy-p-tert-butylcalix[4]areneH2 [Cax(OH)2(OMe)2] or p-tert-butylcalix[6]areneH6 [Cax[6](OH)6] with alkali metal cations and the chromium complexes [CrCl3(THF)3] or [CrCl2(THF)] (THF = tetrahydrofuran) are described. In particular, the treatment of [Cax(OH)4] with in situ generated M[Cr(Ot-Bu)4] (M = Li or K) affords, after work-up, the complex {[CrCax(O)4(NCMe)]2[Li(THF)]2[Li(NCMe)]2Cl2(μ4-O)}·2.25(MeCN) (1) and two forms of {K(MeCN)x[CrCax(O)4(NCMe)][CrCax(OH)(O)3(NCMe)]}·MeCN (x = 3 or 4) (2), respectively. The potassium salt of [Cax(OH)4] reacts with [CrCl2(THF)] to afford a highly sensitive complex, which on exposure to air gives rise to the compound {[CrCax(O)4K(THF)2]2H(μ-O)(H2O)K(THF)(H2O)(μ-THF)}2·6THF (3), that possesses four chromium calixarene units, two sets of K+ ions that are coordinated in two very different environments together with terminal and bridging THF ligands. The reaction of n-BuLi with [Cax(OH)4], followed by the addition of [CrCl3(THF)3] affords, after work-up, the complex {Cr[μ-Cax(OH)(O)3](NCMe)}2·4Me2CO·0.5H2O (4). Complex 4 is also available via the hydrolysis of complex 1. Interaction of [Cax(OH)2(OMe)2] with NaH or n-BuLi in THF affords, following the addition of [CrCl3(THF)3], the demethylated dimer {Cr[μ-Cax(OH)(O)3](NCMe)}2·4MeCN (5), which is a different solvate of 4, or the monomeric salt {Cax(O)2(OMe)2CrCl2[Li(NCMe)2]}·2MeCN (6), respectively. The reaction of 1,3-dipropoxy-p-tert-butylcalix[4]areneH2, [Cax(OH)2(On-Pr)2], with n-BuLi followed by [CrCl3(THF)3] affords the monomeric complex [CrCl2Cax(O)2(On-Pr)2Li(NCMe)2]·3MeCN (7). Interaction of the mono-methoxy ligand [Cax(OH)3(OMe)] with n-BuLi in diethyl ether followed by addition of [CrCl3(THF)3] in THF affords, upon work-up, the complex [CrCax(OMe)(O)3(NCMe)]2·MeCN (8). Interaction of p-tert-butylcalix[6]areneH6 [Cax[6](OH)6] with Na[Cr(Ot-Bu)4] (formed in situ from [CrCl3(THF)3] and excess NaOt-Bu) affords the complex {CrCax[6](O)3(OH)3Na(NCMe)2(μ-OH)}2·4MeCN (9). Complexes 1–9 have been structurally characterised; for 3 and 8, it was necessary to use synchrotron radiation. Screening of 1–9 for ethylene polymerisation using either methylaluminoxane (MAO) or dimethylaluminium chloride (DMAC) as co-catalyst afforded only very poor catalytic activities (≤ 1 g mmol−1 hr−1bar−1)." @default.
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• W2037442270 date "2009-01-01" @default.
• W2037442270 modified "2023-10-12" @default.
• W2037442270 title "New structural motifs in chromium(<scp>iii</scp>) calix[4 and 6]arene chemistry" @default.
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• W2037442270 doi "https://doi.org/10.1039/b813313a" @default.
• W2037442270 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/19322496" @default.
• W2037442270 hasPublicationYear "2009" @default.
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