dichloro(1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene)germanium(II) | 1000619-32-8

• 英文名称: dichloro(1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene)germanium(II)
• 英文别名: GeCl₂(1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene)；GeCl₂(^MeIⁱPr)
• CAS: 1000619-32-8
• 化学式: C₁₁H₂₀Cl₂GeN₂
• 分子量: 323.789
• InChiKey: MCOFMPBBUXOIBZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 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：

  三甲基溴硅烷 、 dichloro(1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene)germanium(II) 以 苯 为溶剂， 以71%的产率得到2-(dibromogermyl)-1,3-diisopropyl-4,5-dimethyl-2,3-dihydro-1H-imidazole
  参考文献：
  名称：

  Synthesis and Structure of N-Heterocyclic Carbene Complexes of Germanium(II)

  摘要：

  The synthesis and structural characterization of a series of N-heterocyclic carbene (NHC) complexes of GeR1R2 are reported, where R-1 = R-2 = Mes (Mes = 2,4,6-trimethylphenyl) (1), R-1 = R-2 = F (5), R-1 = R-2 = Br (6), R-1 = Cl, R-2 = OTf (OTf = O3SCF3) (7), R-1 = R-2 = (OBu)-Bu-t (10), and R-1 = R-2 = NCS (11). The bond length between the carbenic carbon and the germanium is observed to vary in accordance with the pi-donating ability of the substituent on Ge. Efforts to synthesize stable complexes with small alkyl or aryl substituents were not successful; evidence for oligomerization of the GeR2 fragment is presented. The reaction between 1 and 3 (R-1 = R-2 = Cl) resulted in the formation of an NHC-coordinated germylgermylene (13). The H-1 NMR spectra of 3-7, 10, and 11 display broad signals at room temperature. To rationalize the H-1 NMR spectra, mechanisms for conformational interchange, as well as intermolecular exchanges, are discussed.

  DOI：

  10.1021/om800368d
• 作为产物：
  描述：

  以 苯 为溶剂， 生成 dichloro(1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene)germanium(II)
  参考文献：
  名称：

  Reactivity Studies of N-Heterocyclic Carbene Complexes of Germanium(II)

  摘要：

  The chemistry of three N-heterocyclic carbene (NHC) complexes of GeR2, where R = Cl (1), (OBu)-Bu-1 (2), Mes (3) (Mes = 2,4,6-trimethylphenyl), toward 2,3-dimethylbutadiene (DMB), 3,5-di-tert-butylorthoquinone, methyl iodide, pivalic acid, and benzophenone is reported. Upon heating, 2 and 3 cyclize with DMB to yield a germacyclopentene and free NHC. In contrast, 1 does not react with DMB. PB1PBE/6-311+G(d,p) model chemistry shows that the cycloaddition reactions of NHC-GeX2 (X = F, Cl) with butadiene are not thermodynamically favorable. 3,5-Di-tert-butylorthoquinone reacts rapidly with 1-3 to form cyclic products; in the case of 1 and 2, the NHC remains coordinated to the germanium, resulting in a hypervalent species. Compounds 1-3 react with methyl iodide by displacement of in each case [NHC-GeR2Me](+) is produced. Only compound 3 reacts in a controlled fashion with pivalic acid; both 1:1 and 1:2 adducts were characterized. Benzophenone failed to react with 1 or 2 but did undergo cycloaddition with 3. In comparison with uncomplexed GeR2 species, the NHC-GeR2 complexes are less reactive. The prospect of using NHC-GeR2 as a synthon for GeR2 appears to be reaction specific.

  DOI：

  10.1021/om100059z

文献信息

• Iron Complexes with Stabilized Germylenes: Syntheses and Characterizations
  作者：Mohammad El Ezzi、Tibor-Gabor Kocsor、Florian D’Accriscio、David Madec、Sonia Mallet-Ladeira、Annie Castel

  DOI：10.1021/om500903g

  日期：2015.2.9

  nonacarbonyl has been investigated. These germylenes act as two-electron carbene-like ligands and lead to stable germylene iron complexes by exchange reaction of a carbonyl ligand. Whereas the amidinato chloro germylenes lead to stable complexes, a bis(iron germylene) oxide was obtained from the bis-amidinato germylene. The reactions of NHC-stabilized germylenes (5a,b) with Fe2(CO)9 were also explored

  研究了of基（1a，b，2a）或NHC（5a，b）稳定的锗（II）化合物对二铁九碳二烯的反应性。这些亚二甲苯基充当两电子卡宾样配体，并通过羰基配体的交换反应形成稳定的亚二甲基苯铁配合物。the胺基氯亚甲基苯可生成稳定的络合物，而双亚氨基氨基亚甲基萘可制得双（亚铁亚铁）氧化物。NHC稳定的亚二甲基亚砜（5a，b）与Fe 2（CO）9的反应还进行了探索，得到了亚甲基的供体-受体复合物。通过单晶X射线衍射结构测定，可以对所有锗铁络合物进行充分表征（1 H和13 C NMR和IR）。
• A Germanium(II)-Centered Dication
  作者：Paul A. Rupar、Viktor N. Staroverov、Paul J. Ragogna、Kim M. Baines

  DOI：10.1021/ja0775725

  日期：2007.12.1

  The dicationic 42+ complex with three N-heterocyclic carbenes coordinated to a germanium center is reported. The complex was characterized by 1H NMR and FT Raman spectroscopy, and the structure was determined by single-crystal X-ray diffraction. Electronic structure calculations reveal a partial positive charge at germanium and that the germanium lone pair shows no evidence for π bonding.

  报道了具有与锗中心配位的三个 N-杂环卡宾的双阳离子 42+ 复合物。该配合物通过1H NMR和FT拉曼光谱表征，结构由单晶X射线衍射确定。电子结构计算显示锗处带有部分正电荷，并且锗孤对没有显示 π 键合的证据。
• A Nickel Complex Containing a Pyramidalized, Ambiphilic Pincer Germylene Ligand
  作者：Takahito Watanabe、Yumi Kasai、Hiromi Tobita

  DOI：10.1002/chem.201903069

  日期：2019.10.22

  3-diisopropyl-4,5-dimethylimidazol-2-ylidene) with Ni(cod)2 gave pincer germylene complex Ni[Geo-(PiPr2 )C6 H4 }2 ](Me IiPr) (2), in which the Ge center of 2 is significantly pyramidalized. Theoretical calculation on 2 predicted the ambiphilicity of the germanium center, which was confirmed by reactivity studies. Thus, complex 2 reacted with both Lewis base Me IMe (Me IMe=1,3,4,5-tetramethylimidazol-2-ylidene)

  N杂环卡宾（NHC）稳定的PGeP型亚甲基Ge o-（PiPr2）C6 H4} 2⋅MeIiPr（1）（Me IiPr = 1,3-二异丙基-4,5-二甲基咪唑-2-亚叉基）与Ni（cod）2生成夹钳的亚ylene基络合物Ni [Ge o-（PiPr2）C6 H4} 2]（Me IiPr）（2），其中2的Ge中心显着呈锥体状。对2的理论计算预测了锗中心的歧义性，这已通过反应性研究得到了证实。因此，配合物2与路易斯碱Me IMe（Me IMe = 1,3,4,5-四甲基咪唑-2-亚基）和路易斯酸BH3⋅SMe2在锗中心反应，得到加合物Ni [Ge o-（ PiPr2）C6 H4} 2⋅MeIMe]（Me IiPr）（3）和Ni [Ge o-（PiPr2）C6 H4} 2⋅ ]（Me IiPr）（4）。此外，前者在室温下缓慢转化为双核络合物Ni2 [Ge o-（PiPr2）C6 H4}
• NHC-Stabilized Silagermenylidene: A Heavier Analogue of Vinylidene
  作者：Anukul Jana、Volker Huch、David Scheschkewitz

  DOI：10.1002/anie.201306780

  日期：2013.11.11

  low‐valent Group 14 elements, namely silagermenylidene A, is achieved by reduction of Tip2SiCl2 and NHC⋅GeCl2 (Tip=2,4,6‐iPr3C6H2; NHC=1,3‐diisopropyl‐4,5‐dimethylimidazol‐2‐ylidene). The potential of A as a synthon is demonstrated by the formal [2+2] cycloaddition with phenylacetylene to afford NHC‐stabilized cyclic germylene B.

  稳定亚乙烯基类似物：一种新的化合物类低原子价14族元素，即silagermenylidene的第一代表性的合成甲，通过还原提示的实现2的SiCl 2和NHC⋅GeCl 2（提示= 2,4,6- i Pr 3 C 6 H 2； NHC = 1,3-二异丙基-4,5-二甲基咪唑-2-亚基）。的电位甲作为合成子是由正式[2 + 2]环加成与苯基乙炔得到NHC稳定环状锗烯证明乙。
• A stable heavier group 14 analogue of vinylidene
  作者：Arnab Rit、Jesús Campos、Haoyu Niu、Simon Aldridge

  DOI：10.1038/nchem.2597

  日期：2016.11

  Vinylidene (H2C=C) is a member of the family of compounds of composition CH (and isomeric with ethyne, HC≡CH), but it has been observed only transiently—with a lifetime in the region of 0.1 ns. Indeed, no simple (non-base-stabilized) compounds of the type R2E=E have been characterized structurally for any of the group 14 elements. Here we show that by employing the bulky and strongly electron-donating

  亚乙烯基（H 2 C = C）是组成CH（与乙炔，HCyneCH的异构体）的化合物家族的成员，但只能短暂观察到，寿命在0.1 ns左右。实际上，对于第14组元素中的任何一种，都没有在结构上表征出R 2 E = E类型的简单（非碱稳定的）化合物。在这里，我们表明通过使用庞大且强供电子的硼基配体（HCDippN）2 B（Dipp，2,6- i Pr 2 C 6 H 3），一种简单的单体二锗亚乙烯基化合物（硼基）2GeGe可以合成，并且在室温下稳定。它通过对称Ge 0化合物K 2 [（硼基）GeGe（硼基）]的双电子化学氧化形成及其随后的反应化学性质（例如，与H 2）均与高取代基不稳定性和1,1和1,2替代模式的可访问性。[（HCDippN）2 B] 2 GeGe的结构和计算研究表明，弱的Ge-Ge双键（其π成分有助于占据最高的分子轨道（HOMO））以Ge为中心的孤对作为HOMO- 1。