Department of Chemistry, Texas Christian University, Box 298860, Fort Worth, Texas 76129, USA.
Inorg Chem. 2009 Nov 2;48(21):10312-25. doi: 10.1021/ic9014477.
A series of bismuth(III) and antimony(III) complexes supported by silicon-containing calix[5]arene ligands were synthesized and fully characterized by NMR, X-ray, IR, mp, UV/vis, and elemental analysis. Reaction of the para-tert-butylcalix[5]arene [(t)BuC5(H)(5)] disodium salt, Na(2) x (t)BuC5(H)(3), with 1 equiv of R(2)SiCl(2) (R = Me, (i)Pr, Ph, CH=CH(2)) or treatment of the (t)BuC5(H)(5) lower rim monobenzyl ether [(t)BuC5(Bn)(H)(4)] in a 1:1 ratio with Me(2)Si(NMe(2))(2) yields the (t)BuC5(SiRR')(H)(3) (1-5) and (t)BuC5(Bn)(SiMe(2))(H)(2) (6) ligands, respectively. The (1)H NMR spectra of the (t)BuC5(SiRR')(H)(3) (1-5) ligands show three pairs of doublets and three singlets for the (t)Bu peaks, consistent with a C(s) symmetry. In the case of the (t)BuC5(Bn)(SiMe(2))(H)(2) (6) ligand, the presence of the monobenzyl group changes the (1)H NMR patterns to indicate a C(1) symmetry. Treatment of (t)BuC5(SiRR')(H)(3) (1-5) or (t)BuC5(Bn)(SiMe(2))(H)(2) (6) with 1 equiv of M(O(t)Bu)(3) (M = Bi, Sb) or Sb(NMe(2))(2) readily yields metalated products of the type [M{(t)BuC5(SiRR')}] (7-16) and [MX{(t)BuC5(Bn)(SiMe(2))}] (X = O(t)Bu, (NMe(2))(2)) (17-19), respectively. All monometallic complexes [M{(t)BuC5(SiRR')}] (7-19) display excellent solubility in organic solvents including pentane and hexane. The (1)H NMR patterns for complexes 7-16 are consistent with a 1,2- or 1,3-alternate conformation while complexes [MX{(t)BuC5(Bn)(SiMe(2))}] (17-19) display patterns for a C(1) symmetry. All crystals show monomeric structures. Ligand (t)BuC5(SiPh(2))(H)(3) (3) displays a distorted cone conformation while the presence of the monobenzyl ether in (t)BuC5(Bn)(SiMe(2))(H)(2) (6) forces a partial cone conformation. Complexes 7-19 all display a distorted 1,2-alternate conformation with the metal centers displaying coordination numbers of three, four or five. No Si...M interactions were observed.
一系列含硅杯[5]芳烃配体的铋(III)和锑(III)配合物被合成并通过 NMR、X 射线、IR、mp、UV/vis 和元素分析进行了充分的表征。对对叔丁基杯[5]芳烃[(t)BuC5(H)(5)]二钠盐 Na(2) x (t)BuC5(H)(3)与 1 当量的 R(2)SiCl(2) (R = Me、(i)Pr、Ph、CH=CH(2))或处理下的反应(t)BuC5(H)(5)下边缘单苄基醚[(t)BuC5(Bn)(H)(4)]以 1:1 与 Me(2)Si(NMe(2))(2)的比例得到(t)BuC5(SiRR')(H)(3) (1-5)和(t)BuC5(Bn)(SiMe(2))(H)(2) (6)配体，分别。(t)BuC5(SiRR')(H)(3) (1-5)配体的(1)H NMR 谱显示出(t)Bu 峰的三个双峰和三个单峰，这与 C(s)对称性一致。对于(t)BuC5(Bn)(SiMe(2))(H)(2) (6)配体，单苄基的存在改变了(1)H NMR 图谱，表明其具有 C(1)对称性。(t)BuC5(SiRR')(H)(3) (1-5)或(t)BuC5(Bn)(SiMe(2))(H)(2) (6)与 1 当量的 M(O(t)Bu)(3) (M = Bi、Sb)或 Sb(NMe(2))(2)反应很容易得到[M{(t)BuC5(SiRR')}] (7-16)和[MX{(t)BuC5(Bn)(SiMe(2))}] (X = O(t)Bu、(NMe(2))(2)) (17-19)的金属化产物，分别。所有单金属配合物[M{(t)BuC5(SiRR')}] (7-19)在包括戊烷和己烷在内的有机溶剂中都具有优异的溶解性。配合物 7-16 的(1)H NMR 图谱与 1,2-或 1,3-交替构象一致，而配合物[MX{(t)BuC5(Bn)(SiMe(2))}] (17-19)显示出 C(1)对称性的图谱。所有晶体均表现出单体结构。配体(t)BuC5(SiPh(2))(H)(3) (3)显示出扭曲的锥形构象，而(t)BuC5(Bn)(SiMe(2))(H)(2) (6)中存在单苄基醚则迫使部分锥形构象。配合物 7-19 均显示出扭曲的 1,2-交替构象，金属中心的配位数为三、四或五。没有观察到 Si...M 相互作用。
