Ge(tBu2bzam)Cl | 1076189-13-3

• 英文名称: Ge(tBu2bzam)Cl
• 英文别名: N,N’-di-tert-butylchloro(phenylamidinate)germanium(II)；N,N′-di-tert-butyl(phenylamidinate)chlorogermylene；N,N'-ditert-butyl(phenylamidinato)chlorogermylene；chlorogermylene；Ge(N,N′-bis(tertbutyl)benzamidinate)Cl；Ge(^tBu₂bzam)Cl；[(PhC(NtBu)₂)GeCl]
• CAS: 1076189-13-3
• 化学式: C₁₅H₂₃ClGeN₂
• 分子量: 339.404
• InChiKey: YMWXYKYNWMNNAL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  Ge(tBu2bzam)Cl 在 potassium 作用下， 以 四氢呋喃 为溶剂， 以35%的产率得到[PhC(NtBu)2Ge]2
  参考文献：
  名称：

  RGe(I)Ge(I)R Compound (R = PhC(NtBu)₂) with a Ge−Ge Single Bond and a Comparison with the Gauche Conformation of Hydrazine

  摘要：

  This article reports the reduction of the chloride [PhC(NtBu)(2)]GeCl with potassium in THF to afford the reddish crystals of [PhC(NtBu)(2)](2)Ge-2 (2). The molecule of 2 contains a Ge-Ge bond. The X-ray structure and DFT calculation indicate that the Ge-Ge bond possesses an unusual gauche-bent geometry. The Ge-Ge bond length in 2 is 2.570 angstrom, which is very close to the single Ge-Ge interaction (2.61 angstrom) but significantly longer than that for typical digermenes, R2GeGeR2 (2.21-2.51 angstrom) and the two structurally characterized digermynes (2.2850 angstrom and 2.2060 angstrom), which proves that there is no multiple bond character in 2.

  DOI：

  10.1021/om800714f
• 作为产物：
  描述：

  germanium(II) chloride dioxane 、 N,N′-二叔丁基碳二亚胺 、 苯基锂 以 乙醚 为溶剂， 生成 Ge(tBu2bzam)Cl
  参考文献：
  名称：

  RGe(I)Ge(I)R Compound (R = PhC(NtBu)₂) with a Ge−Ge Single Bond and a Comparison with the Gauche Conformation of Hydrazine

  摘要：

  This article reports the reduction of the chloride [PhC(NtBu)(2)]GeCl with potassium in THF to afford the reddish crystals of [PhC(NtBu)(2)](2)Ge-2 (2). The molecule of 2 contains a Ge-Ge bond. The X-ray structure and DFT calculation indicate that the Ge-Ge bond possesses an unusual gauche-bent geometry. The Ge-Ge bond length in 2 is 2.570 angstrom, which is very close to the single Ge-Ge interaction (2.61 angstrom) but significantly longer than that for typical digermenes, R2GeGeR2 (2.21-2.51 angstrom) and the two structurally characterized digermynes (2.2850 angstrom and 2.2060 angstrom), which proves that there is no multiple bond character in 2.

  DOI：

  10.1021/om800714f

文献信息

• Highly Electron-Rich Pincer-Type Iron Complexes Bearing Innocent Bis(metallylene)pyridine Ligands: Syntheses, Structures, and Catalytic Activity
  作者：Daniel Gallego、Shigeyoshi Inoue、Burgert Blom、Matthias Driess

  DOI：10.1021/om500966t

  日期：2014.12.8

  neutral bis(metallylene)pyridine pincer-type [ENE] ligands (E = SiII, GeII) were synthesized, and their coordination chemistry and reactivity toward iron was studied. First, the unprecedented four-coordinate complexes κ2E,E′-[ENE]FeCl2 were isolated. Unexpectedly and in contrast to other related pyridine-based pincer-type Fe(II) complexes, the N atom of pyridine is reluctant to coordinate to the Fe(II)

  合成了第一个中性双（亚甲基）吡啶钳型[ ENE ]配体（E = Si II，Ge II），并研究了它们的配位化学和对铁的反应性。首先，空前的四配位配合物κ 2 E，E ' - [ENE]的FeCl 2中分离得到。出乎意料的是，与其他相关的吡啶基钳型Fe（II）配合物相反，吡啶的N原子由于E原子的σ供体强度增加而不愿意与Fe（II）配位。这种协调模式。随后的还原的κ 2的Si，硅' - [SiNSi]的FeCl 2与KC 8在PMe 3的存在下或[ ENE ]配体使用Fe（PMe 3）4的直接反应产生了高度富电子的铁（0）络合物[ENE] Fe（PMe 3）2。铁中心的还原实质上改变了其配位特征，如[SiNSi] Fe（PMe 3）2的单晶X射线衍射分析结果所示。后者的铁中心表现出伪正方形的金字塔（PSQP）配位环境，其中配位（吡啶）N→Fe键，三甲基膦配体占据顶部。对于Fe（0）低自旋络合
• Oxidative Addition Versus Substitution Reactions of Group 14 Dialkylamino Metalylenes with Pentafluoropyridine
  作者：Prinson P. Samuel、Amit Pratap Singh、Sankaranarayana Pillai Sarish、Julia Matussek、Ina Objartel、Herbert W. Roesky、Dietmar Stalke

  DOI：10.1021/ic302344a

  日期：2013.2.4

  germanium is the first report of this kind. The Sn(II) fluoride obtained has an elongated Sn–F bond length and can be used as a good fluorinating agent. The compounds were characterized by multinuclear NMR spectroscopy, mass spectrometry, elemental analysis, and X-ray structural analysis. Single crystal X-ray structural analysis of the tin fluoride shows an asymmetric dimer with weak interactions.

  合成了苯甲酰胺酸盐配体支持的+2氧化态的第14组元素（Si，Ge，Sn）的二烷基氨基化合物，并用五氟吡啶处理。观察到两种不同的反应模式，这取决于金属原子和金属上取代基的碱性。五氟吡啶在Si（II）和Ge（II）原子上进行氧化加成反应，而在NMe 2的Sn（II）原子上进行取代基团由对氟的五氟吡啶发生。单独的锗对激活C-F键是第一个此类报道。所获得的Sn（II）氟化物具有延长的Sn-F键长度，可以用作良好的氟化剂。化合物通过多核NMR光谱，质谱，元素分析和X射线结构分析进行表征。氟化锡的单晶X射线结构分析显示出具有弱相互作用的不对称二聚体。
• Bis(silylenyl)- and Bis(germylenyl)-Substituted Ferrocenes: Synthesis, Structure, and Catalytic Applications of Bidentate Silicon(II)-Cobalt Complexes
  作者：Wenyuan Wang、Shigeyoshi Inoue、Stephan Enthaler、Matthias Driess

  DOI：10.1002/anie.201202175

  日期：2012.6.18

  Strong bite: The two respective SiII and GeII centers in ferrocene‐containing bis(silylene) and bis(germylene) ligands 1 can serve as excellent σ donors, as shown in the formation of Co complexes 2 (see scheme, Cp=η5‐cyclopentadienyl). Unexpectedly, only the bis(silylene)–Co complex 2 is a precatalyst for the [2+2+2] cycloaddition of phenylacetylene and MeCN, possibly because of a stronger coordination

  强力咬咬：含二茂铁的双（甲硅烷基）和双（亚锗烯）配体1中的两个Si II和Ge II中心可作为出色的σ供体，如Co配合物2的形成所示（请参见方案，Cp =η 5-环戊二烯基）。出乎意料的是，只有双（甲硅烷基）-Co配合物2是苯乙炔和MeCN [2 + 2 + 2]环加成反应的前催化剂，可能是因为Ge II供体中心对Co的更强配位作用。
• Pushing the σ-Donor Strength in Iridium Pincer Complexes: Bis(silylene) and Bis(germylene) Ligands Are Stronger Donors than Bis(phosphorus(III)) Ligands
  作者：Andreas Brück、Daniel Gallego、Wenyuan Wang、Elisabeth Irran、Matthias Driess、John F. Hartwig

  DOI：10.1002/anie.201205570

  日期：2012.11.12

  Breaking the donor limits: The remarkable coordination chemistry of ECHE (E=Si, Ge) ligands with Group 9 metals (Ir, Rh) and their application in catalytic CH borylation of arenes was investigated. The spectroscopic and structural features of the first [ECE] iridium complexes show the stronger σ‐donating properties of the divalent Si and Ge pincer ligands compared to analogous PIII‐based ligands.

  打破了供体的限制：ECHE（E =硅，锗）的显着的配位化学配位体与第9族金属（铱，铑）以及它们在催化C应用程序芳烃h的硼基化进行了研究。第一种[ECE]铱配合物的光谱和结构特征表明，与类似的基于P III的配体相比，二价Si和Ge钳形配体具有更强的σ供体性质。
• Indirect and Direct Grafting of Transition Metals to Siliconoids
  作者：Nadine E. Poitiers、Luisa Giarrana、Kinga I. Leszczyńska、Volker Huch、Michael Zimmer、David Scheschkewitz

  DOI：10.1002/anie.202001178

  日期：2020.5.25

  transition-metal fragments that are readily accessible from the ligato-lithiated Si6 siliconoid (1Li) and Cp2 MCl2 (M=Zr, Hf). Charge-neutral siliconoid ligands with pending tetrylene functionality were prepared by the reaction of amidinato chloro tetrylenes [PhC(NtBu)2 ]ECl (E=Si, Ge, Sn) with 1Li, thus confirming the principal compatibility of such low-valent functionalities with the unsaturated Si6

  不饱和的电荷中性硅团簇（类硅酮）作为分子和元素块之间的气相中间体非常重要。使用稳定的锆茂和ha茂取代的衍生物，我们在此报告了包含直接键合的过渡金属片段的第一个示例，这些片段很容易从连接锂化的Si6硅酮（1Li）和Cp2 MCl2（M = Zr，Hf）中获得。通过pending胺基氯代四甲苯[PhC（NtBu）2] ECl（E = Si，Ge，Sn）与1Li的反应制备了具有待处理的四甲苯官能团的电荷中性硅酮配体，从而证实了这种低价官能团与不饱和Si6团簇支架。四甲苯/硅酮杂化物的显着的供体特性使其与Fe（CO）4片段配位。