[Cp(THF)Yb(μ-η3:η1-SC6H4N=C(NH(i)Pr)N(i)Pr)]2 | 912276-72-3

• 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: [Cp(THF)Yb(μ-η3:η1-SC6H4N=C(NH(i)Pr)N(i)Pr)]2
• 英文别名: cyclopenta-1,3-diene;2-[N,N'-di(propan-2-yl)carbamimidoyl]azanidylbenzenethiolate;oxolane;ytterbium(3+)
• CAS: 912276-72-3
• 化学式: C₄₄H₆₄N₆O₂S₂Yb₂
• 分子量: 1119.24
• InChiKey: UBESCMJPRJUREX-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  11.12
• 重原子数：
  56
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  71.2
• 氢给体数：
  2
• 氢受体数：
  10

反应信息

• 作为产物：
  描述：

  N,N'-二异丙基碳二亚胺 、 [Cp2Yb(o-H2NC6H4S)]2*2THF 以 四氢呋喃 为溶剂， 以70%的产率得到[Cp(THF)Yb(μ-η3:η1-SC6H4N=C(NH(i)Pr)N(i)Pr)]2
  参考文献：
  名称：

  含有邻氨基苯硫酚酸酯配体的有机酚衍生物对碳二亚胺的反应性

  摘要：

  已经合成了一系列含有邻氨基硫酚盐配体的镧系茂衍生物，并且已经研究了它们对碳二亚胺的反应性。的反应Ñ，Ñ “-diisopropylcarbodiimide（我PRN Ç Ñ我PR）与的[Cp 2镱（ø -H 2 NC 6 H ^ 4 S）] 2 ·2THF（CP = C 5 H ^ 5）（1）产生一个中心对称的二聚物，的[Cp（THF）镱（μ- η 3：η 1 -SC 6 ħ 4 ñ C（NH我PR）N我Pr）] 2（2），表明相邻的NH 2基团可以加到碳二亚胺的C N双键上，并且一个环戊二烯基基团被消除。[Cp 2 Dy（o -H 2 NC 6 H 4 S）] 2 ·3THF，通过Cp 3 Ln与邻氨基硫酚的质子分解而获得，与2或1当量的i反应PRN Ç Ñ我镨在THF中在室温下，得到的部分氨基加成产物CpDy（THF）[μ- η 3：η 1 -SC 6 ħ 4 Ñ C（NH我PR）N我PR）]（μ-

  DOI：

  10.1021/om060491h

文献信息

• 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。