Sánchez Mario, Harvey Melanie J, Nordstrom Fredrick, Parkin Sean, Atwood David A
Department of Chemistry, The University of Kentucky, Lexington, KY 40506-0055, USA.
Inorg Chem. 2002 Oct 21;41(21):5397-402. doi: 10.1021/ic020101t.
Salen complexes of the heavy alkaline-earth metals, calcium and strontium, were prepared by the reaction of various salen(t-Bu)H(2) ligands with the metals in ethanol. Six new calcium and strontium compounds, [Ca(salen(t-Bu))(HOEt)(2)(thf)] (1), [Ca(salen(t-Bu))(HOEt)(2)] (2), [Ca(salpen(t-Bu))(HOEt)(3)] (3), [Ca(salophen(t-Bu))(HOEt)(thf)] (4), [Sr(salen(t-Bu))(HOEt)(3)] (5), and [Sr(salophen(t-Bu))(HOEt)(thf)(2)] (6), were formed in this way with the quatridentate Schiff-base ligands N,N'-bis(3,5-di-tert-butylsalicylidene)ethylenediamine (salen(t-Bu)H(2)), N,N'-bis(3,5-di-tert-butylsalicylidene)-1,3-propanediamine (salpen(t-Bu)H(2)), and N,N'-o-phenylenebis(3,5-di-tert-butylsalicylideneimine (salophen(t-Bu)H(2)). Initially, ammonia solutions of the metals were combined with the salen(t-Bu)H(2) ligands, and in the reaction of strontium with salen(t-Bu)H(2), the unusual tetrametallic cluster (OC(6)H(2)(t-Bu)(2)CHN(CH(2))(2)NH(2))Sr(mu(3)-salean(t-Bu)H(2))Sr(mu(3)-OH) (7) was produced (salean(t-Bu)H(4) = N,N'-bis(3,5-di-tert-butyl-2-hydroxybenzyl)ethylenediamine). In this compound, the imine bonds of the salen(t-Bu)H(2) ligand were reduced to form the known ligands salean(t-Bu)H(4) and (HO)C(6)H(2)(t-Bu)(2)CHN(CH(2))(2)NH(2). Compounds 1, 5, 6, and 7 were structurally characterized by single-crystal X-ray diffraction. Crystal data for 1 (C(44)H(74)CaN(2)O(6)): triclinic space group P(-)1, a = 8.3730(10) A, b = 14.8010(10) A, c = 18.756(2) A, alpha = 72.551(10) degrees, beta = 81.795(10) degrees, gamma = 78.031(10) degrees, Z = 2. Crystal data for 5 (C(38)H(64)SrN(2)O(5)): monoclinic space group P2(1)/c, a = 23.634(3) A, b = 8.4660(10) A, c = 24.451(3) A, beta = 101.138(10) degrees, Z = 4. Crystal data for 6 (C(46)H(67)N(2)O(5)Sr): orthorhombic space group P2(1)2(1)2(1), a = 10.5590(2) A, b = 16.2070(3) A, c = 26.7620(6) A, Z = 4. Crystal data for 7 (C(98)H(156)N(8)O(8)Sr(4)): triclinic space group P(-)1, a = 14.667(1) A, b = 15.670(1) A, c = 18.594(2) A, alpha = 92.26(1) degrees, beta = 111.84(1) degrees, gamma = 117.12(1) degrees, Z = 4.
通过各种N,N'-双(3,5-二叔丁基水杨醛)乙二胺(salen(t-Bu)H₂)配体与重碱土金属钙和锶在乙醇中反应，制备了它们的Salen配合物。用四齿席夫碱配体N,N'-双(3,5-二叔丁基水杨醛)乙二胺(salen(t-Bu)H₂)、N,N'-双(3,5-二叔丁基水杨醛)-1,3-丙二胺(salpen(t-Bu)H₂)和N,N'-邻亚苯基双(3,5-二叔丁基水杨醛亚胺)(salophen(t-Bu)H₂)以这种方式形成了六种新的钙和锶化合物，即[Ca(salen(t-Bu))(HOEt)₂(thf)] (1)、[Ca(salen(t-Bu))(HOEt)₂] (2)、[Ca(salpen(t-Bu))(HOEt)₃] (3)、[Ca(salophen(t-Bu))(HOEt)(thf)] (4)、[Sr(salen(t-Bu))(HOEt)₃] (5)和[Sr(salophen(t-Bu))(HOEt)(thf)₂] (6)。最初，将金属的氨溶液与salen(t-Bu)H₂配体混合，在锶与salen(t-Bu)H₂的反应中，生成了不寻常的四金属簇[(OC₆H₂(t-Bu)₂CHN(CH₂)₂NH₂)Sr(μ₃-salean(t-Bu)H₂)Sr(μ₃-OH)]₂ (7)（salean(t-Bu)H₄ = N,N'-双(3,5-二叔丁基-2-羟基苄基)乙二胺）。在该化合物中，salen(t-Bu)H₂配体的亚胺键被还原，形成了已知的配体salean(t-Bu)H₄和(HO)C₆H₂(t-Bu)₂CHN(CH₂)₂NH₂。通过单晶X射线衍射对化合物1、5、6和7进行了结构表征。化合物1 (C₄₄H₇₄CaN₂O₆)的晶体数据：三斜晶系空间群P(-)1，a = 8.3730(10) Å，b = 14.8010(10) Å，c = 18.756(2) Å，α = 72.551(10)°，β = 81.795(10)°，γ = 78.031(10)°，Z = 2。化合物5 (C₃₈H₆₄SrN₂O₅)的晶体数据：单斜晶系空间群P2(1)/c，a = 23.634(3) Å，b = 8.4660(10) Å，c = 24.451(3) Å，β = 101.138(10)°，Z = 4。化合物6 (C₄₆H₆₇N₂O₅Sr)的晶体数据：正交晶系空间群P2(1)2(1)2(1)，a = 10.5590(2) Å，b = 16.2070(3) Å，c = 26.7620(6) Å，Z = 4。化合物7 (C₉₈H₁₅₆N₈O₈Sr₄)的晶体数据：三斜晶系空间群P(-)1，a = 14.667(1) Å，b = 15.670(1) Å，c = 18.594(2) Å，α = 92.26(1)°，β = 111.84(1)°，γ = 117.12(1)°，Z = 4。
