Mendoza-Espinosa Daniel, Hanna Tracy A
Department of Chemistry, Texas Christian University, P.O. Box 298860, Fort Worth, Texas 76129, USA.
Dalton Trans. 2009 Jul 14(26):5211-25. doi: 10.1039/b903943k. Epub 2009 May 26.
A series of calix[5]arene bismuth(III) and antimony(III) mono- and bimetallic complexes were synthesized and fully characterized by NMR, X-ray, IR, mp, UV-Vis and elemental analysis. Reaction of p-tert-butylcalix[5]arene (tBuC5(H)5) trianionic salts M'3.tBuC5(H)2 (M'=Li, Na, K) with MCl3 (M=Bi, Sb) yielded monometallic complexes [Bi{tBuC5(H)2}] 1 and [Sb{tBuC5(H)2}] 2, respectively. 1H NMR spectra of both complexes showed two remaining OH groups available for further reactivity. Alternatively, complexes 1 and 2 can be obtained by reacting tBuC5(H)5 in a 1:1 ratio with M(OtBu)3, but the yields are lower. When the tBuC5(H)5 lower rim monobenzyl ether [tBuC5(Bn)(H)4] is treated in a 1:1 ratio with Bi(OtBu)3, the monometallic complex [Bi{tBuC5(Bn)(H)}]2 3 is prepared. If, however, [tBuC5(Bn)(H)4] reacts with Sb(NMe2)3 or Sb(OtBu)3 in a 1:2 ratio the production of the bimetallic complex [Sb2O{tBuC5(Bn)}] 4 is observed. p-Benzylcalix[5]arene (BnC5(H)5) reacts with excess Bi(OtBu)3 to produce the bimetallic complex [Bi2O{BnC5(H)}]2 5. 1H NMR spectra of 5 display patterns characteristic for a cone conformer in solution. Treatment of calix[5]arene [HC5(H)5] with one equivalent of Bi[N(SiMe3)2]3 or with 0.75 equivalents of Sb(NMe2)3 yields bimetallic complexes [Bi2O{HC5(H)}] 6 and [Sb2O{HC5(H)}] 7, respectively. The reactivity of monometallic complexes 1 and 2 was tested in order to investigate the availability of their remaining OH groups. Treatment of 1 with Bi(OtBu)3 at ambient temperature yields bimetallic complex [Bi2O{tBuC5(H)}]2 8 while the reaction of complex 2 with Sb(OtBu)3 in a 1:1 ratio produces complex [Sb2O{tBuC5(H)}] 9. The crystal structures of the monometallic bismuth complexes 1 and 3 display dimeric units with the calixarene ligands in distorted cone and "paco-in" conformations, respectively. Complexes 4, 7 and 9 are all monomeric units, displaying [(RO)2Sb]2(micro-O) cores and the calixarene ligands in 1,2-alternate conformation. The dimeric units of bimetallic complexes 5 and 8 contain Bi4O2(OR)8 core structures that force the calixarene ligands to adopt a flattened cone conformation.
合成了一系列杯[5]芳烃铋（III）和锑（III）的单金属及双金属配合物，并通过核磁共振（NMR）、X射线、红外光谱（IR）、熔点（mp）、紫外可见光谱（UV-Vis）和元素分析对其进行了全面表征。对叔丁基杯[5]芳烃（tBuC5(H)5）的三阴离子盐M'3.tBuC5(H)2（M' = Li、Na、K）与MCl3（M = Bi、Sb）进行反应，分别得到单金属配合物[Bi{tBuC5(H)2}] 1和[Sb{tBuC5(H)2}] 2。两种配合物的1H NMR谱显示有两个剩余的OH基团可用于进一步反应。另外，配合物1和2也可以通过叔丁基杯[5]芳烃（tBuC5(H)5）与M(OtBu)3以1:1的比例反应得到，但产率较低。当对叔丁基杯[5]芳烃下缘的单苄基醚[tBuC5(Bn)(H)4]与Bi(OtBu)3以1:1的比例反应时，制备得到单金属配合物[Bi{tBuC5(Bn)(H)}]2 3。然而，如果[tBuC5(Bn)(H)4]与Sb(NMe2)3或Sb(OtBu)3以1:2的比例反应，则会观察到双金属配合物[Sb2O{tBuC5(Bn)}] 4的生成。对苄基杯[5]芳烃（BnC5(H)5）与过量的Bi(OtBu)3反应，生成双金属配合物[Bi2O{BnC5(H)}]2 5。5的1H NMR谱显示出溶液中锥形构象的特征峰。用一当量的Bi[N(SiMe3)2]3或0.75当量的Sb(NMe2)3处理杯[5]芳烃[HC5(H)5]，分别得到双金属配合物[Bi2O{HC5(H)}] 6和[Sb2O{HC5(H)}] 7。为了研究单金属配合物1和2中剩余OH基团的反应活性，对其进行了测试。在室温下，用Bi(OtBu)3处理1，得到双金属配合物[Bi2O{tBuC5(H)}]2 8，而配合物2与Sb(OtBu)3以1:1的比例反应，则生成配合物[Sb2O{tBuC5(H)}] 9。单金属铋配合物1和3的晶体结构分别显示出二聚体单元，杯芳烃配体分别处于扭曲的锥形和“paco-in”构象。配合物4、7和9均为单体单元，显示出[(RO)2Sb]2(μ-O)核心结构，杯芳烃配体处于1,2-交替构象。双金属配合物5和8的二聚体单元包含Bi4O2(OR)8核心结构，迫使杯芳烃配体采取扁平的锥形构象。
