La2(O-2,6-i-Pr2C6H3)6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: La2(O-2,6-i-Pr2C6H3)6
• 化学式: 6C₁₂H₁₇O*2La
• 分子量: 1341.41
• InChiKey: QOLBTOALCRGQDS-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  3.01
• 重原子数：
  14.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  23.06
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  La2(O-2,6-i-Pr2C6H3)6 、 cesium 2,6-diisopropylphenoxide 以 四氢呋喃 、 甲苯 为溶剂， 以37%的产率得到Cs[La(O-2,6-i-Pr₂C₆H₃)4]
  参考文献：
  名称：

  Alkali Metal Induced Structural Changes in Complexes Containing Anionic Lanthanum Aryloxide Moieties. X-ray Crystal Structures of (THF)La(OAr)₂(μ-OAr)₂Li(THF), (THF)La(OAr)₂(μ-OAr)₂Na(THF)₂, and CsLa(OAr)₄ (Ar = 2,6-i-Pr₂C₆H₃)

  摘要：

  Reaction of La-2(OAr)(6) (1, Ar = 2,6-i-Pr2C6H3) with 2 equiv of LiOAr in THF produces the lanthanum tetrakis(aryloxide) salt (THF)La(OAr)(2)(mu-OAr)(2)Li(THF) (2). A similar reaction employing NaOAr leads to isolation of the analogous sodium salt (THF)La(OAr)(2)(mu-OAr)(2)Na(THF)(2) (3). 1 reacts with 2 equiv of cesium aryloxide in THF to yield the base-free cesium salt CsLa(OAr)(4) (4). Compounds 2, 3, and 4 have been characterized by H-1 NMR and IR spectroscopy, microanalysis, and single-crystal X-ray diffraction studies. The overall molecular geometry of 2 comprises a five-coordinate La metal center coordinated by four aryloxide ligands and one THF ligand in a somewhat distorted trigonal bipyramidal geometry and a three-coordinate Li cation which is coordinated to the oxygen atoms of two aryloxide ligands as well as a single THF ligand. La-O bond lengths average 2.208(3) and 2.384(3) Angstrom for terminal and bridging aryloxide Ligands, respectively, while the average Li-O(aryloxide) bond distance is 1.866(10) Angstrom. The molecular geometry of 3 is similar to that observed in 2, with a five-coordinate La metal center displaying a distorted trigonal bipyramidal geometry in which a THF ligand and an aryloxide ligand occupy axial positions. Two of the aryloxide ligands on the La metal center bridge to a sodium cation, which completes its coordination sphere by coordination of two additional molecules of THF. La-O bond lengths average 2.227(6) and 2.333(5) Angstrom for terminal and bridging aryloxide ligands, respectively, while the average Na-OAr bond distance is 2.350(6) Angstrom. The ipso carbon atom of one of the bridging aryloxide ligands is directed toward the fifth coordination site of the sodium cation at a distance of 3.085(9) Angstrom. The solid state structure of CsLa(OAr)(4), (4) features alternating tetrahedral [La(OAr)(4)](-) anions (La-O = 2.241(6) Angstrom (ave.)) and Cs+ cations held in an extended structure by means of cesium-pi-arene interactions, resulting in the formation of a quasi one-dimensional infinite chain structure. The cesium environment in 4 consists exclusively of multihapto Cs-C interactions (Cs-C range 3.696(7)-3.847(7) Angstrom), with no Cs-O contacts of less than 4.649 Angstrom. Crystal data for 2 (at -100 degrees C): orthorhombic space group Pbca, a = 20.091(3) Angstrom, b = 19.983(2) Angstrom, c = 27.288(2) Angstrom, V = 10956 Angstrom(3), Z = 8, D-calc = 1.202 g cm(-3). Crystal data for 3 (at -100 degrees C): orthorhombic space group Pbca, a = 26.035(3) Angstrom, b = 20.771(4) Angstrom, c = 26.441(3) Angstrom, V = 14299 Angstrom(3), Z = 8, D-calc = 1.174 g cm(-3). Crystal data for 4 (at -100 degrees C): monoclinic space group C2/c, a = 21.261(2) Angstrom, b = 22.616(3) Angstrom, c = 20.740(2) Angstrom, beta = 108.126(7)degrees, V = 9478 Angstrom(3), Z = 8, D-calc = 1.465 g cm(-3).

  DOI：

  10.1021/ic9510472

文献信息

• New homoleptic anionic aryloxolanthanide(III) complexes with unusual coordination trapping of the alkali-metal counter ions
  作者：David L. Clark、Glen B. Deacon、Tiecheng Feng、Rebecca V. Hollis、Brian L. Scott、Brian W. Skelton、John G. Watkin、Allan H. White

  DOI：10.1039/cc9960001729

  日期：——

  The complex Cs2[La(OAr)5]}(Ar = C6H3Pri2-2,6), from LaCl3 or La2(OAr)6 and CsOAr in tetrahydrofuran, has an unprecedented polymeric structure in which five-coordinate [La(OAr)5]2– anions are bonded to caesium in a three- dimensional network solely by Ar–Cs π bonds, whilst Na[Nd(Odpp)4]}(dpp = C6H3Ph2-2,6), from NdCl3 and NaOdpp in 1,3,5-tri-tert-butylbenzene at 300 °C, has an unexpected monomeric structure with sodium bonded to three oxygens and encapsulated by three phenyl groups of [Nd(Odpp)4]–.

  在四氢呋喃中，由LaCl3或La2(OAr)6和CsOAr组成的复合物Cs2[La(OAr)5]}(Ar = C6H3Pri2-2,6)具有前所未有的聚合结构，其中五配位[La(OAr)5]2-阴离子通过Ar-Csπ键与铯原子以三维网络结合，而在1,3,5-三叔丁基苯中，由NdCl3和NaOdpp在300°C下形成的Na[Nd(Odpp)4]}(dpp = C6H3Ph2-2,6)具有出人意料的单体结构，钠原子与三个氧原子结合，并被[Nd(Odpp)4]–的三个苯基团包裹。
• Alkali Metal Induced Structural Changes in Complexes Containing Anionic Lanthanum Aryloxide Moieties. X-ray Crystal Structures of (THF)La(OAr)₂(μ-OAr)₂Li(THF), (THF)La(OAr)₂(μ-OAr)₂Na(THF)₂, and CsLa(OAr)₄ (Ar = 2,6-<i>i</i>-Pr₂C₆H₃)
  作者：David L. Clark、Rebecca V. Hollis、Brian L. Scott、John G. Watkin

  DOI：10.1021/ic9510472

  日期：1996.1.1

  Reaction of La-2(OAr)(6) (1, Ar = 2,6-i-Pr2C6H3) with 2 equiv of LiOAr in THF produces the lanthanum tetrakis(aryloxide) salt (THF)La(OAr)(2)(mu-OAr)(2)Li(THF) (2). A similar reaction employing NaOAr leads to isolation of the analogous sodium salt (THF)La(OAr)(2)(mu-OAr)(2)Na(THF)(2) (3). 1 reacts with 2 equiv of cesium aryloxide in THF to yield the base-free cesium salt CsLa(OAr)(4) (4). Compounds 2, 3, and 4 have been characterized by H-1 NMR and IR spectroscopy, microanalysis, and single-crystal X-ray diffraction studies. The overall molecular geometry of 2 comprises a five-coordinate La metal center coordinated by four aryloxide ligands and one THF ligand in a somewhat distorted trigonal bipyramidal geometry and a three-coordinate Li cation which is coordinated to the oxygen atoms of two aryloxide ligands as well as a single THF ligand. La-O bond lengths average 2.208(3) and 2.384(3) Angstrom for terminal and bridging aryloxide Ligands, respectively, while the average Li-O(aryloxide) bond distance is 1.866(10) Angstrom. The molecular geometry of 3 is similar to that observed in 2, with a five-coordinate La metal center displaying a distorted trigonal bipyramidal geometry in which a THF ligand and an aryloxide ligand occupy axial positions. Two of the aryloxide ligands on the La metal center bridge to a sodium cation, which completes its coordination sphere by coordination of two additional molecules of THF. La-O bond lengths average 2.227(6) and 2.333(5) Angstrom for terminal and bridging aryloxide ligands, respectively, while the average Na-OAr bond distance is 2.350(6) Angstrom. The ipso carbon atom of one of the bridging aryloxide ligands is directed toward the fifth coordination site of the sodium cation at a distance of 3.085(9) Angstrom. The solid state structure of CsLa(OAr)(4), (4) features alternating tetrahedral [La(OAr)(4)](-) anions (La-O = 2.241(6) Angstrom (ave.)) and Cs+ cations held in an extended structure by means of cesium-pi-arene interactions, resulting in the formation of a quasi one-dimensional infinite chain structure. The cesium environment in 4 consists exclusively of multihapto Cs-C interactions (Cs-C range 3.696(7)-3.847(7) Angstrom), with no Cs-O contacts of less than 4.649 Angstrom. Crystal data for 2 (at -100 degrees C): orthorhombic space group Pbca, a = 20.091(3) Angstrom, b = 19.983(2) Angstrom, c = 27.288(2) Angstrom, V = 10956 Angstrom(3), Z = 8, D-calc = 1.202 g cm(-3). Crystal data for 3 (at -100 degrees C): orthorhombic space group Pbca, a = 26.035(3) Angstrom, b = 20.771(4) Angstrom, c = 26.441(3) Angstrom, V = 14299 Angstrom(3), Z = 8, D-calc = 1.174 g cm(-3). Crystal data for 4 (at -100 degrees C): monoclinic space group C2/c, a = 21.261(2) Angstrom, b = 22.616(3) Angstrom, c = 20.740(2) Angstrom, beta = 108.126(7)degrees, V = 9478 Angstrom(3), Z = 8, D-calc = 1.465 g cm(-3).