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Ammonium, alkylammonium, and amino acid complexes of a hexacopper fluoro-metallacrown cavitand

机译:六铜氟金属内酰胺空穴分子的铵,烷基铵和氨基酸配合物

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摘要

Reaction of CuF2 with one equivalent of 3{5}-(pyrid-2-yl)-5{3}-(tertbutyl)pyrazole (HL) and excess NH4OH in MeOH affords crystalline [NH4{Cu(mu-F)(mu-L)}(6)(CH2Cl2)2]HF2 in moderate yield. This compound contains the 12-MC-6 metallacrown [{Cu-(mu-F)(mu-L)}6] (1) with a NH4(+) ion at its center, and CH2Cl2 molecules complexed in bowl-shaped cavities above and below the CU6F6 ring. Similar reactions using the bases MeNH2, glycine, L-alanine or beta-alanine afforded solvated crystals of [1(H3NMe)(2)]Cl-2, [1-(gly)(2)], [1(L-ala)(2)], and [1(beta-ala)(2)], respectively. The metallacrown 1 in these products contains methylammonium and zwitterionic amino-acid guests in its two bowl-shaped cavities; each of the amino acids hydrogen-bonds to three F atoms. A related reaction using 1,6-diaminohexane resulted in fixation Of CO2 from the air to give solvated [1(H3NC6H12NHCO2)(2)], again with a zwitterionic guest. NMR, ESI-MS and UV/vis measurements suggest that the metallacrown 1 retains its integrity in several organic solvents, although it is unclear to what extent guest binding takes place in solution.
机译:CuF2与一当量的3 {5}-(吡啶-2-基)-5 {3}-(叔丁基)吡唑(HL)和过量的NH4OH在MeOH中的反应生成晶体[NH4 {Cu(mu-F)(mu -L)}(6)(CH2Cl2)2] HF2的收率中等。该化合物包含12-MC-6金属lac [{Cu-(mu-F)(mu-L)} 6](1),中心具有NH4(+)离子,以及在碗形空腔中络合的CH2Cl2分子CU6F6环上方和下方。使用碱MeNH2,甘氨酸,L-丙氨酸或β-丙氨酸进行的类似反应得到[1(H3NMe)(2)] Cl-2,[1-(gly)(2)],[1(L-丙氨酸)的溶剂化晶体)(2)]和[1(beta-ala)(2)]。这些产品中的金属漆1在其两个碗形空腔中包含甲基铵和两性离子氨基酸客体;每个氨基酸都氢键合至三个F原子。使用1,6-二氨基己烷的相关反应导致空气中CO2的固着,再次以两性离子客体生成溶剂化的[1(H3NC6H12NHCO2)(2)]。 NMR,ESI-MS和UV / vis测量表明,金属漆1在几种有机溶剂中保持其完整性,尽管尚不清楚溶液中客体结合的程度。

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