三甲基铟

三甲基铟
IUPAC名
Trimethylindium
系统名
Trimethylindigane[1]
别名 三甲基铟烷
识别
CAS号 3385-78-2  checkY
PubChem 76919
ChemSpider 69370
SMILES
 
  • C[In](C)C
InChI
 
  • 1/3CH3.In/h3*1H3;/rC3H9In/c1-4(2)3/h1-3H3
InChIKey IBEFSUTVZWZJEL-SGQDGSKVAB
EINECS 222-200-9
性质
化学式 InC
3
H
9
摩尔质量 159.922 g·mol⁻¹
外观 白色晶体
密度 1.568 g cm−3 (at 20 °C)
熔点 88 °C(361 K)
沸点 134 °C(407 K)(在 101 °C(214 °F;374 K)以上分解)
溶解性 反应
热力学
ΔfHm298K 150.5-169.7 kJ mol−1
危险性
GHS危险性符号
《全球化学品统一分类和标签制度》(简称“GHS”)中易燃物的标签图案《全球化学品统一分类和标签制度》(简称“GHS”)中腐蚀性物质的标签图案
GHS提示词 Danger
H-术语 H250, H260, H261, H314, H318
P-术语 P210, P222, P223, P231+232, P260, P264, P280, P301+330+331, P302+334, P303+361+353, P304+340, P305+351+338, P310, P321
主要危害 可自燃
相关物质
其他阳离子 三甲基硼
三甲基铝
三甲基镓
三甲基铊
相关化学品 三乙基铟
若非注明,所有数据均出自标准状态(25 ℃,100 kPa)下。

三甲基铟,简称TMITMIn,是一种有机铟化合物,化学式 In(CH3)3。它是无色、可自燃的固体。[2]它的结构不像三甲基铝,但与三甲基镓类似,三甲基铟是单体。[3]

制备

三甲基铟可以由三氯化铟甲基锂反应而成。[2][4]

InCl3 + 3 LiMe → Me3In.OEt2 + 3 LiCl

性质

相较于三甲基铝三甲基镓,InMe3 是一种较弱的路易斯酸。它与仲和仲形成加合物。[5]它和一种三嗪配体 (PriNCH2)3 形成的配合物含有六配位铟, C-In-C 键角为 114°-117°。它与三齿配体形成三个长键,N-In-N 角为 48.6°,长 In-N 键的键长为 278 pm。[6]

结构

气态的InMe3 是单体,为平面三角形结构。它在溶液中是四聚体。[5] 在固态时,三甲基铟有两种结构,一种是四方晶系的。另一种是2005年发现,密度较低的三方晶系,[7]可以由 InMe3己烷重结晶而成。

四方的InMe3的苯溶液是四聚体,在这些四聚体之间有桥接原子连接。每个铟原子都是五配位的,为扭曲三角双锥结构。三个最短的键的键长为 216 pm 都在水平方向,而轴向的In-C 键较长,为 308 pm(四聚体里的 InMe3)或 356 pm(四聚体和四聚体之间的桥接键)。[8] 固态GaMe3TlMe3也有类似的结构。[8]三甲基铟的固态结构使得它的熔点(89°-89.8 °C)比三乙基铟(-32 °C)大得多。[5]

三方的InMe3则是环状六聚体,结构为环己烷构象。其中的铟原子也是五配位,In-C 平均键长为 216.7 pm ,几乎和四方晶系一样。它的轴向键则为302.8 pm(这些键将InMe3单体连接为六聚体)或 313.4 pm(六聚体和六聚体之间的桥接键)。[7]

危险性

三甲基铟会自燃[9]

参考资料

  1. ^ Trimethylindium - PubChem Public Chemical Database. The PubChem Project. USA: National Center for Biotechnology Information. Descriptors Computed from Structure. 27 March 2005 [21 September 2011]. (原始内容存档于2012-11-04). 
  2. ^ 2.0 2.1 Bradley, D. C.; Chudzynska, H. C.; Harding, I. S. Trimethylindium and Trimethylgallium. Inorganic Syntheses. 1997, 31: 67–74. doi:10.1002/9780470132623.ch8. 
  3. ^ Greenwood, Norman Neill; Earnshaw, Alan. Chemistry of the elements. 2016. ISBN 978-0-7506-3365-9. OCLC 1040112384 (英语). 
  4. ^ Main Group compounds in Inorganic Syntheses, vol 31, Schultz, Neumayer, Marks; Ed., Alan H. Cowley, John Wiley & Sons, Inc., 1997, ISBN 0471152889
  5. ^ 5.0 5.1 5.2 CVD of compound semiconductors, Precursor Synthesis, Development and Applications, Anthony C. Jones, Paul O'Brien, John Wiley & Sons, 2008, ISBN 3527292942
  6. ^ Greenwood, N. N.; Earnshaw, A. Chemistry of the Elements 2nd. Oxford:Butterworth-Heinemann. 1997: 263. ISBN 0-7506-3365-4. 
  7. ^ 7.0 7.1 Lewiński, Janusz; Zachara, Janusz; Starowieyski, Kazimierz B.; Justyniak, Iwona; Lipkowski, Janusz; Bury, Wojciech; Kruk, Przemysław; Woźniak, Robert. A Second Polymorphic Form of Trimethylindium: Topology of Supramolecular Architectures of Group 13 Trimethyls. Organometallics. 2005, 24 (20): 4832–4837. ISSN 0276-7333. doi:10.1021/om050386s. 
  8. ^ 8.0 8.1 Inorganic Chemistry, (2d edition), Catherine E. Housecroft, Alan G. Sharpe, Pearson Education, 2005, ISBN 0130399132 , ISBN 978-0130399137
  9. ^ Chemistry of Materials (2000); doi:10.1021/cm990497f

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