Dichloroosmium;isocyanomethane;1,3,5-trimethylbenzene | 136033-81-3

• 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: Dichloroosmium;isocyanomethane;1,3,5-trimethylbenzene
• CAS: 136033-81-3
• 化学式: C₁₁H₁₅Cl₂NOs
• 分子量: 422.353
• InChiKey: XYVPFTYSCQYCDX-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  4.52
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  4.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  Dichloroosmium;isocyanomethane;1,3,5-trimethylbenzene 在 KI 作用下， 以 丙酮 为溶剂， 以90%的产率得到diiodoosmium;isocyanomethane;1,3,5-trimethylbenzene
  参考文献：
  名称：

  [[mes] Os（CNR）Cl2]的制备以及甲基异氰化物配合物与有机锂和格利雅试剂的反应。[[mes] Os（：C（NHCH3）C6H5）（C6H5）2]的X射线晶体结构

  摘要：

  The isocyanide complexes [(mes)Os(CNR)Cl2] (2-4) are prepared almost quantitatively from [(mes)OsCl2]n (1) and CNR in dichloromethane. Reactions of 2 (R = CH3) with CH3Li and C6H5Li in hydrocarbon-ether give the dimethyl and diphenyl derivates [(mes)OsR2(CNCH3)] (5, 6) in excellent yields. Treatment of 2 with CH3MgI leads to the formation of a mixture of [(mes)OsCH3(CNCH3)I] (7) and [(mes)Os(CNCH3)I2] (9), which can be separated by column chromatography. Analogously, from 2 and C6H5MgI, both [(mes)OsC6H5(CNCH3)I] (8) and 9 have been obtained. In contrast, reaction of 2 with C6H5MgBr gives, besides [(mes)OsC6H5(CNCH3)Br] (11), the carbene complex [(mes)Os(= C(NHCH3)C6H5)(C6H5)2] (10) as the main product. The X-ray crystal structure of 10 has been determined (monoclinic space group P2(1)/n with a = 12.402 (3) angstrom, b = 14.237 (2) angstrom, c = 13.622 (2) angstrom, beta = 91.54 (1)-degrees). The molecule possesses a piano-stool configuration with an Os-C(carbene) distance of 1.992 (5) angstrom.

  DOI：

  10.1021/om00055a053
• 作为产物：
  描述：

  (mesitylene)osmium dichloride 、 甲胩 以 二氯甲烷 为溶剂， 以80%的产率得到Dichloroosmium;isocyanomethane;1,3,5-trimethylbenzene
  参考文献：
  名称：

  [[mes] Os（CNR）Cl2]的制备以及甲基异氰化物配合物与有机锂和格利雅试剂的反应。[[mes] Os（：C（NHCH3）C6H5）（C6H5）2]的X射线晶体结构

  摘要：

  The isocyanide complexes [(mes)Os(CNR)Cl2] (2-4) are prepared almost quantitatively from [(mes)OsCl2]n (1) and CNR in dichloromethane. Reactions of 2 (R = CH3) with CH3Li and C6H5Li in hydrocarbon-ether give the dimethyl and diphenyl derivates [(mes)OsR2(CNCH3)] (5, 6) in excellent yields. Treatment of 2 with CH3MgI leads to the formation of a mixture of [(mes)OsCH3(CNCH3)I] (7) and [(mes)Os(CNCH3)I2] (9), which can be separated by column chromatography. Analogously, from 2 and C6H5MgI, both [(mes)OsC6H5(CNCH3)I] (8) and 9 have been obtained. In contrast, reaction of 2 with C6H5MgBr gives, besides [(mes)OsC6H5(CNCH3)Br] (11), the carbene complex [(mes)Os(= C(NHCH3)C6H5)(C6H5)2] (10) as the main product. The X-ray crystal structure of 10 has been determined (monoclinic space group P2(1)/n with a = 12.402 (3) angstrom, b = 14.237 (2) angstrom, c = 13.622 (2) angstrom, beta = 91.54 (1)-degrees). The molecule possesses a piano-stool configuration with an Os-C(carbene) distance of 1.992 (5) angstrom.

  DOI：

  10.1021/om00055a053

文献信息

• A series of mono- and dihydrido- as well as mono- and dimethylosmium(II) complexes containing [(mes)Os(CNR)] as a building block
  作者：H Werner、U Wecker

  DOI：10.1016/s0022-328x(99)00394-0

  日期：2000.1

  The dihydridoosmium(II) complexes [(mes)OsH2(CNR)] (7-10) were prepared in excellent yield from the dichloroosmium(II) precursors [(mes)OsCl2(CNR)] upon treatment with 10% magnesium amalgam in THF in the presence of ethanol. Under similar conditions, the methylisocyanide derivative [(mes)OsH2(CNMe)] (6) as well as the monohydrido compounds [(mes)OsH(X)(CNMe)] (11, 13) were obtained. The same methodology using [(mes)OsCl(C6H5)(CNR)] as the starting material was applied for the preparation of the hydrido(phenyl)osmium(II) complexes [(mes)OsH(C6H5)(CNR)] (19-23) which were also isolated in almost quantitative yield. Treatment of these complexes with HCl in CH2Cl2 at -78 degrees C led to the cleavage of the osmium-phenyl but not the osmium-hydride bond. Reactions of [(mes)OsCl2(CNR)] with MeLi/LiCl gave exclusively the dimethylosmium(II) compounds [(mes)Os(CH3)(2)(CNR)] (29-32) while the corresponding reactions with MeLi/LiI afforded a mixture of 29-32 and the monomethyl derivatives [(mes)OsI(Me)(CNR)] (26, 33-35). A cyclic carbeneosmium(II) complex 37 was obtained from [(mes)OsCl2(CNPh)] and MeLi/LiI followed by treatment with deactivated Al2O3. The etheneosmium(0) compound [(mes)Os(C2H4)(CNMe)] (38) was prepared from the dimethylosmium(II) precursor 29 and briefly investigated as starting material for photochemical C-H activation reactions. (C) 2000 Elsevier Science S.A. All rights reserved.
• Novel synthesis and vibrational analysis of (arene)osmium(II) complexes of the type [(C6H3(CH3)3)OsH2(L)]
  作者：T. Polzer、A. Ellebracht、W. Kiefer、U. Wecker、H. Werner

  DOI：10.1016/0022-328x(92)83415-e

  日期：1992.10

  The dihydridoosmium(II) complexes [(mes)OSH2(L)] (mes = C6H3(CH3)3; L = CO, 4; CNCH3, 5) have been prepared in nearly quantitative yields from [(mes)OsCl2(L)] (L = CO, 1; CNCH 3, 2) and Mg/Hg in THF in the presence of C2H5OH as a proton source. These complexes are suitable for studies of C-H activation by UV irradiation in solution. The FT-IR and Raman spectra of 4 and 5 have been recorded in the range between 400 and 3300 cm-1 and between 100 and 3300 cm-1, respectively; a complete assignment of the observed vibrational modes is presented, supported by polarized Raman spectra. The Os-ligand vibrations of half sandwich complexes of this type have been determined for the first time. A normal coordinate analysis of the osmium-ligand modes has been performed by treating the ring ligand as a point mass. Force constants and potential energy distributions are given.