1-methyl-2-nitroso-ortho-carborane | 16872-08-5

• 英文名称: 1-methyl-2-nitroso-ortho-carborane
• 英文别名: 1,2-C2B10H10-1-NO-2-CH3；methyl nitrosocarborane；(Me)(o-carboranyl)(NO)
• CAS: 16872-08-5
• 化学式: C₃H₁₃B₁₀NO
• 分子量: 187.252
• InChiKey: SPEQYXQZEQTYCJ-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：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  1-methyl-2-nitroso-ortho-carborane 在 盐酸 、 tin 作用下， 生成 1,2-C2B10H10-1-NHOH-2-CH3
  参考文献：
  名称：

  Zakharkin, L. I.; Zhigareva, G. G., Zhurnal Obshchei Khimii, 1975, vol. 45, p. 1268 - 1275

  摘要：

  DOI：
• 作为产物：
  描述：

  正丁基锂 、 1-methyl-ortho-carborane 以 乙二醇二甲醚 、 乙醚 为溶剂， 以63%的产率得到bis(2-methyl-ortho-carboranyl)amine
  参考文献：
  名称：

  New synthetic and structural studies on nitroso-ortho-carboranes RCB10H10CNO and bis(ortho-carboranyl)amines (RCB10H10C)2NH (R=Ph or Me)

  摘要：

  Improved procedures are reported for the preparation of nitroso-carboranes RCb degrees NO (Cb degrees = 1,2-C2B10H10; R = Ph, Me at cage carbon C2) in 44-77% yield, and of dicarboranylamines (RCb degrees)(2)NH in 55-65% yield by reactions between the lithio-carboranes, RCb degrees Li and nitrosyl chloride, NOCl, in cold mixtures of diethyl ether and either pentane (for RCb degrees NO) or dimethoxyethane (for (RCb degrees)(2)NH). Deprotonation of the amines by (KOBu)-Bu-t in toluene in the presence of 18-crown-6, (CH2CH2O)(6), affords the salts [K(18-crown-6)](+)[(RCb degrees)(2)N](-), X-ray crystal structures of PhCb degrees NO, (PhCb degrees)(2)NH, (MeCb degrees)(2)NH and [K(18-crown-6)](+)[(PhCb degrees)(2)N](-) are described, and the bonding implications of their cage C center dot center dot center dot C distances (1.68, 1.80, 1.75 and 1.99 angstrom, respectively) are discussed. These species provide further striking examples of the remarkable capacity of the ortho-carborane cage to act as a sensitive indicator of the pi-donor characteristics of ligands attached to its cage carbon atoms. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2008.12.014

文献信息

• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: B: B Comp.SVol.1/3, 13.18.3.2, page 213 - 227
  作者：

  DOI：——

  日期：——
• Trends in ortho-carboranes 1-X-2-R-1,2-C2B10H10 (R=Ph, Me) bearing an exo-CN-bonded substituent group (X=NO, NNR′ or NHR′′)
  作者：Mark A. Fox、Richard J. Peace、William Clegg、Mark R.J. Elsegood、Kenneth Wade

  DOI：10.1016/j.poly.2009.04.041

  日期：2009.8

  The preparation and crystal structures of four ortho-carboranyl-nitrogen compounds, PhCb degrees N=N(C6H4Me-4) (1), PhCb degrees NHNH(C6H4Me-4) (2), MeCb degrees NHNHPh (3) and PhCb degrees NHOH (4) (Cb degrees = 1,2-C2B10H10; nitrogen groups at cage carbon C1, Ph or Me at C2), the last as a 1,4-dioxane solvate, are reported. Comparisons of their structures with those of other ortho-carboranyl-nitrogen systems studied earlier reveal further correlations between their cage C-C and exo-C-N bond distances and bond orders. Substituent orientations and bond distances (cage C1-C2, exo-C1-N) in RCb degrees NHR '' systems (R = Ph or Me at C2) are consistent with dative pi-bonding from a nitrogen lone pair into the cage carbon p-AO otherwise responsible for cage C1-C2 sigma-bonding. Their C1-C2 bond distances are remarkably sensitive to the planar (sp(2)) or pyramidal (sp(3)) nature of the NHR '' group. The N=O and N=NR' residues in RCb degrees X prefer to be orientated in plane with the cage C1-C2 in contrast to the RCb degrees NHR '' systems. Correlations between their cage C-C and exo-C-N bond distances and the B-11 NMR chemical shifts of their antipodal boron atoms reflect the pi-bonding characteristics of the nitrogen substituent. (C) 2009 Elsevier Ltd. All rights reserved.