Gd(Cp)₃ | 1080547-33-6

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: Gd(Cp)₃
• 英文别名: Tris(cyclopentadienyl)gadolinium(III), 99.9% trace metals basis
• CAS: 1080547-33-6
• 化学式: C₁₅H₁₅Gd
• 分子量: 352.534
• InChiKey: ZCFWIGYKHNDYOA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.06
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  2-氨基-4,6-二甲基嘧啶 、 Gd(Cp)₃ 以 甲苯 为溶剂， 以44%的产率得到[(η5-Cp)2Gd(2-amino-4,6-dimethylpyrimidine-H)]2
  参考文献：
  名称：

  有机镧系元素（III）酰胺的结构和磁性研究。

  摘要：

  系列二聚有机镧系元素（Cp2Ln {2-NH-4,6-Me2pm}] 2 [Ln = Nd（1），Gd（2），Dy（3），报道了Yb（4）和pm =嘧啶]，它们是由2-氨基-4,6-二甲基嘧啶被相应的镧系元素三环戊二烯去质子化而形成的。[{Cp2Yb（2-NH-4-MeO-6-MeOpm）（2）（mu3-O）（YbCp）]（5）的合成和结构是在类似的质子化反应中但在不定水存在下形成的，也有报道。

  DOI：

  10.1039/b514470a
• 作为产物：
  描述：

  di-μ-methyl-bis(η-cyclopentadienyl)gadolinium(III)dimethylaluminium(III) 以 neat (no solvent) 为溶剂， 生成 Gd(Cp)₃
  参考文献：
  名称：

  Alkyl-bridged complexes of the d- and f-block elements. Part 1. Di-µ-alkyl-bis(η-cyclopentadienyl)metal(III)dialkylaluminium(III) complexes and the crystal and molecular structure of the ytterbium methyl species

  摘要：

  DOI：

  10.1039/dt9790000045

文献信息

• Group 4 Metal and Lanthanide Complexes in the Oxidation State +3 with Tris(trimethylsilyl)silyl Ligands
  作者：Rainer Zitz、Johann Hlina、Henning Arp、Dominik Kinschel、Christoph Marschner、Judith Baumgartner

  DOI：10.1021/acs.inorgchem.9b00866

  日期：2019.5.20

  A number of paramagnetic silylated d1 group 4 metallates were prepared by reaction of potassium tris(trimethylsilyl)silanide with group 4 metallates of the type K[Cp2MCl2] (M = Ti, Zr, Hf). The outcomes of the reactions differ for all three metals. While for the hafnium case the expected complex [Cp2HfSi(SiMe3)3}2]− was obtained, the analogous titanium reaction led to a product with two Si(H)(SiMe3)2

  通过三(三甲基甲硅烷基)硅烷化钾与K[Cp 2 MCl 2 ]型(M = Ti、Zr、Hf)的第4族金属化物的反应，制备了许多顺磁性甲硅烷基化d 1 4族金属化物。所有三种金属的反应结果都不同。虽然对于铪情况，获得了预期的配合物 [Cp 2 HfSi(SiMe 3 ) 3 } 2 ] -，但类似的钛反应产生了具有两个 Si(H)(SiMe 3 ) 2配体的产物。与锆的反应导致形成双核富瓦烯桥连络合物。所需的 [Cp 2 ZrSi(SiMe 3 )3 } 2 ] -可以通过用钾还原Cp 2 ZrSi(SiMe 3 ) 3 } 2获得。在三（三甲基甲硅烷基）硅烷化钾与某些镧系元素 Cp 3 Ln（Ln = Ce、Sm、Gd、Ho、Tm）配合物的相关反应中，[Cp 3 Ln Si(SiMe 3 ) 3 ] -与 [18-得到了crown-6·K] +或络离子[18-crown-6·K·Cp
• A novel bonding mode of oximato ligand to a metal; synthesis and X-ray crystal structure of bis[acetone oximatobis(cyclopentadienyl)gadolinium][{(C₅H₅)₂Gd(µ-η^2–ONCMe₂)}₂]
  作者：Zhongzhi Wu、Xigen Zhou、Wei Zhang、Zheng Xu、Xiaozeng You、Xiaoying Huang

  DOI：10.1039/c39940000813

  日期：——

  Reaction of [Cp3Gd](Cp = C5H5) with acetone oxime in THF at room temp. results in the formation of a new complex [Cp2Gd(µ-η2–ONCMe2)}2]; X-ray analysis shows an unusual structure with the O–N fragment of ONCMe2 ligand acting as both a bridging and side-on donating group.

  室温下，[Cp 3 Gd]（Cp = C 5 H 5）与丙酮肟在THF中的反应。导致形成新的络合物[Cp 2 Gd（μ- η2 – ONCMe 2）} 2 ]；X射线分析显示，ONCMe 2配体的O–N片段同时充当桥基和侧基捐赠基团，具有不寻常的结构。
• Syntheses, Structure, and Properties of Mixed Cp–Amidinate Rare-Earth-Metal(III) Complexes
  作者：Jun-Feng Liu、Fu-Xing Pan、Shuang Yao、Xue Min、Dongmei Cui、Zhong-Ming Sun

  DOI：10.1021/om400856d

  日期：2014.3.24

  Cp–amidinate rare-earth-metal(III) complexes [Cp2L1LnPhCN] (Ln = Y (1), La (2), Sm (3), Eu (4), Gd (5), Tb (6), Dy (7); L1 = PhC(NSiMe3)2), [Cp2L1Ln] (Ln = Er (8), Yb (9)), and [Cp2L2Ln] (Ln = Y (10), Eu (11), Gd (12), Tb (13), Dy (14), Er (15); L2 = N(t-Bu)C(Ph)N(SiMe3)) were synthesized by treatment of Cp3Ln with lithium amidinates. The phase transition has been observed for compounds 5 and 9 at low

  一族混合的Cp-酰胺基稀土金属（III）配合物[Cp 2 L 1 LnPhCN]（Ln = Y（1），La（2），Sm（3），Eu（4），Gd（5） ，Tb（6），Dy（7）； L 1 = PhC（NSiMe 3）2），[Cp 2 L 1 Ln]（Ln = Er（8），Yb（9））和[Cp 2 L 2 Ln ]（Ln = Y（10），Eu（11），Gd（12），Tb（13），Dy（14），Er（15）; L 2＝ N（t- Bu）C（Ph）N（SiMe 3））是通过用in基锂处理Cp 3 Ln而合成的。在低温（200 K）下观察到化合物5和9的相变。单晶结构分析表明，化合物1，3，4，图5b，6，7，9B，和10 - 15含有两个交错Cp环。与此相反，化合物中观察到两个黯然失色Cp环2，图5a，8和9a。此外，还研究了配合物6的发光性质和配合物7的磁性。
• Synthesis and characterization of dimeric (cyclohexanoneoximato)bis(cyclopentadienyl) lanthanide(III) complexes
  作者：Xiuran Wang、Xu Shen、Baohui Duo

  DOI：10.1016/s0277-5387(00)83181-2

  日期：1992.1

  The reaction Of Cp3Ln (Ln  Pr, Nd, Sm, Gd, Dy, Ho, Er, Y, Tm, Yb; Cp  cyclopentadienyl) with cyclohexanoneoxime in THF results in the formation of [CP2Ln (ONC6H10)]2 in moderate yields. The complexes are considered to be oxygen-bridged dimers on the basis of mass spectral data, and are relatively air-stable. Disproportionation on heating is observed for Ln  Pr, Nd, Sm.

  Cp 3 Ln（LnPr，Nd，Sm，Gd，Dy，Ho，Er，Y，Tm，Yb; Cp环戊二烯基）与环己酮肟在THF中的反应导致形成[CP 2 Ln（ONC 6 H 10）] 2处于中等产量。根据质谱数据，该配合物被认为是氧桥联的二聚体，并且是相对稳定的。对于LnPr，Nd，Sm，观察到加热时的歧化。
• Facile construction of the guanidine substituent or guanidinate anionic ligand through addition of the adjacent amino group to carbodiimide
  作者：Jie Zhang、Liping Ma、Yanan Han、Fuyan Han Zhengxing Zhang、Ruifang Cai、Zhenxia Chen、Xigeng Zhou

  DOI：10.1039/b813711k

  日期：——

  The reaction of N,N′-dicyclohexylcarbodiimide (DCCI) with [Cp2Yb(o-H2NC6H4S)]2 (Cp = C5H5) (1) forms the monomer product Cp2Yb[SC6H4NC(NHCy)2] (2), indicating that the adjacent NH2group can add to the CN double bonds of carbodiimide to construct a neutral guanidine group. When DCCI reacts with [Cp2Y(o-H2NC6H4S)]2·2THF (4), a dimer product [CpY(μ-η2:η1-SC6H4NC(NHCy)NCy)(THF)]2 (5) was isolated, through the amino group addition and cyclopentadienyl elimination. Interestingly, on treatment of 4 with one or two equivalent of iPrNCNiPr at the same conditions gave an amino group partial addition product CpY(THF)[μ-η2:η1-SC6H4NC(NHiPr)NiPr)](μ-η2:η1-SC6H4NH2)YCp2·THF (6), where only one NH2group can add to the CN double bonds of carbodiimide molecule, another one is remained. However, when we extended this reaction to the gadolinium complex, a novel co-crystalline compound Cp2Gd[SC6H4NC(NHCy)2]}·CpGd(THF)[μ-η2:η1-SC6H4NC(NHCy)NCy)][μ-η2:η1-SC6H4NH2]GdCp2·THF} (8) was obtained from the reaction of [Cp2Gd(o-H2NC6H4S)]2 (7) with DCCI. In order to investigate the sequence of addition and the elimination of the cyclopentadienyl group, a deprotonation reaction of the addition product has also been studied. Reaction of CpYb[SC6H4NC(NHiPr)2]2(THF) (9), formed by reaction of Cp3Yb with two equivalent of o-aminothiophenol, and subsequently with 2 equiv. of iPrNCNiPr, with one equiv. of Cp3Yb gave a cyclopentadienyl elimination product [CpYb(μ-η2:η1-SC6H4NC(NHiPr)NiPr)(THF)]2 (3). This result reveals that addition of the NH2group to carbodiimide is prior to the elimination of cyclopentadienyl group. All of new compounds have been characterized by elemental analysis and spectroscopic properties. The solid-state structures of complexes 2, and 5–9 were determined by single-crystal X-ray diffraction.

  N,N′-二环己基碳二亚胺（DCCI）与[Cp2Yb(o-H2NC6H4S)]2（Cp = C5H5）（1）反应生成单体产物 Cp2Yb[SC6H4NC(NHCy)2] (2)，表明相邻的 NH2 基团可与碳二亚胺的 CN 双键相加，形成中性胍基。当 DCCI 与[Cp2Y(o-H2NC6H4S)]2-2THF（4）反应时，通过氨基加成和环戊二烯基消除，分离出二聚体产物[CpY(μ-η2:η1-SC6H4NC(NHCy)NCy)(THF)]2（5）。有趣的是，在相同条件下，用一个或两个等效的 iPrNCNiPr 处理 4 时，得到了氨基部分加成产物 CpY(THF)[μ-η2:η1-SC6H4NC(NHiPr)NiPr)](μ-η2:η1-SC6H4NH2)YCp2-THF（6），其中只有一个 NH2 基团可以加到碳化二亚胺分子的 CN 双键上，另一个则残留下来。然而，当我们将这一反应扩展到钆配合物时，一种新型共晶体化合物 Cp2Gd[SC6H4NC(NHCy)2]}-CpGd(THF)[μ-η2：η1-SC6H4NC(NHCy)NCy)][μ-η2:η1-SC6H4NH2]GdCp2-THF}（8）是由[Cp2Gd(o-H2NC6H4S)]2（7）与 DCCI 反应得到的。为了研究环戊二烯基的加成和消除顺序，还研究了加成产物的去质子化反应。CpYb[SC6H4NC(NHiPr)2]2(THF) (9)是由 Cp3Yb 与两个当量的邻氨基苯硫酚反应生成的，随后又与两个当量的 iPrNCNiPr 反应生成，与一个当量的 Cp3Yb 反应生成环戊二烯基消除产物 [CpYb(μ-η2:η1-SC6H4NC(NHiPr)NiPr)(THF)]2 (3)。这一结果表明，在消除环戊二烯基团之前，NH2 基团已经加入到碳化二亚胺中。所有新化合物都具有元素分析和光谱特性。单晶 X 射线衍射测定了复合物 2 和 5-9 的固态结构。