{molybdenum tetrakis(tert-butyl isocyanide)(η5-7,8-C2B9H11)} | 154203-10-8

• 英文名称: {molybdenum tetrakis(tert-butyl isocyanide)(η5-7,8-C2B9H11)}
• CAS: 154203-10-8
• 化学式: C₂₂H₄₇B₉MoN₄
• 分子量: 560.881
• InChiKey: OCVKIFDEDSZNFX-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：

  {molybdenum tetrakis(tert-butyl isocyanide)(η5-7,8-C2B9H11)} 、 三氟甲烷磺酸甲酯 以 二氯甲烷 为溶剂， 以69%的产率得到{molybdenum tetrakis(tert-butyl isocyanide)(Me)(η5-7,8-C2B9H11)}{CF3SO3}
  参考文献：
  名称：

  钼和钨的双（炔）碳硼烷配合物对叔丁基异氰酸酯的反应性

  摘要：

  Treatment of the complex [Mo(CO)(eta2-MeC2Me)2(eta5-7,8-Me2-7,8-C2B9H9)] (5a) in CH2Cl2 with ca. 4 mol equiv of CNBu(t) affords the compounds [Mo(CO)(CNBu(t))3(eta5-7,8-Me2-7,8-C2B9H9)] (6) and [Mo(CNBu(t))4(eta5-7,8-Me2-7,8-C2B9H9)] (7a). However, reactions between [M(CO)(eta2-MeC2Me)2(eta5-7,8-C2B9H11)] (5b, M = Mo; 5c, M = W) and an excess of CNBu(t) in CH2Cl2 give [M(CNBU(t))4(eta5-7,8-C2B9H11)] (7b, M = Mo; 7c, M = W) and [M{= C[N(H)Bu(t)]C(Me) = C-(Me)[C(O)N(H)Bu(t)]}(CNBU(t))2(ns-7,8-C2B9H11)] (8a, M = Mo; 8b, M = W). The structure of 8b has been established by an X-ray diffraction study. Crystals are triclinic, space group P1BAR (No. 2) with a = 10.913(2) angstrom, b = 11.992(2) angstrom, c = 14.852(2) angstrom, alpha = 73.12(l)-degrees, beta = 82.48(l)-degrees, gamma = 74.138(16)-degrees, and Z = 2. The tungsten atom is ligated by the nido-C2B9H11 cage in the normal pentahapto manner, by two isocyanide molecules (W-CNBu(t) average 2.02 angstrom), and by a vinylcarbene moiety [W = C = 2.018(7) angstrom, W-C = 2.308(8) and 2.335(8) angstrom]. The latter group is formed at the metal center by coupling of one but-2-yne ligand with two isocyanide molecules, followed by reaction with H2O. Methylation of the complex [Mo(CNBU(t))4(eta5-7,8-C2B9H11)] (7b) with CF3SO3Me yields initially the species [MoMe(CNBU(t))4(eta5-7,8-C2B9H11)] [SO3CF3] (9), which rearranges to [Mo(CNBU(t))3{eta2-C(Me) = NBu(t)}(eta5-7,8-C2B9H11)][SO3CF3] (10). The structure of 10 has been determined by X-ray diffraction. Crystals are monoclinic, space group C2/c (No. 15) with a = 41.569(4) angstrom, b = 9.465(2) angstrom, c = 20.381(2) angstrom, beta = 105.616(7)-degrees, and Z = 8. The molybdenum atom is coordinated by a nido-C2B9H11 cage, three isocyanide molecules (Mo-CNBu(t) average 2.11 angstrom), and an eta2-C(Me) = NBu(t) moiety [Mo-C = 2.10(1) angstrom, mo-N = 2.14(1) angstrom]. In addition to the X-ray crystal structure determinations, the IR and NMR data for the new complexes are reported and discussed in relation to their structures.

  DOI：

  10.1021/om00015a016
• 作为产物：
  描述：

  {molybdenum(carbonyl)bis(η2-but-2-yne)(η5-7,8-C2B9H11)} 、 异氰酸叔丁酯 以 二氯甲烷 为溶剂， 以61%的产率得到{molybdenum tetrakis(tert-butyl isocyanide)(η5-7,8-C2B9H11)}
  参考文献：
  名称：

  钼和钨的双（炔）碳硼烷配合物对叔丁基异氰酸酯的反应性

  摘要：

  Treatment of the complex [Mo(CO)(eta2-MeC2Me)2(eta5-7,8-Me2-7,8-C2B9H9)] (5a) in CH2Cl2 with ca. 4 mol equiv of CNBu(t) affords the compounds [Mo(CO)(CNBu(t))3(eta5-7,8-Me2-7,8-C2B9H9)] (6) and [Mo(CNBu(t))4(eta5-7,8-Me2-7,8-C2B9H9)] (7a). However, reactions between [M(CO)(eta2-MeC2Me)2(eta5-7,8-C2B9H11)] (5b, M = Mo; 5c, M = W) and an excess of CNBu(t) in CH2Cl2 give [M(CNBU(t))4(eta5-7,8-C2B9H11)] (7b, M = Mo; 7c, M = W) and [M{= C[N(H)Bu(t)]C(Me) = C-(Me)[C(O)N(H)Bu(t)]}(CNBU(t))2(ns-7,8-C2B9H11)] (8a, M = Mo; 8b, M = W). The structure of 8b has been established by an X-ray diffraction study. Crystals are triclinic, space group P1BAR (No. 2) with a = 10.913(2) angstrom, b = 11.992(2) angstrom, c = 14.852(2) angstrom, alpha = 73.12(l)-degrees, beta = 82.48(l)-degrees, gamma = 74.138(16)-degrees, and Z = 2. The tungsten atom is ligated by the nido-C2B9H11 cage in the normal pentahapto manner, by two isocyanide molecules (W-CNBu(t) average 2.02 angstrom), and by a vinylcarbene moiety [W = C = 2.018(7) angstrom, W-C = 2.308(8) and 2.335(8) angstrom]. The latter group is formed at the metal center by coupling of one but-2-yne ligand with two isocyanide molecules, followed by reaction with H2O. Methylation of the complex [Mo(CNBU(t))4(eta5-7,8-C2B9H11)] (7b) with CF3SO3Me yields initially the species [MoMe(CNBU(t))4(eta5-7,8-C2B9H11)] [SO3CF3] (9), which rearranges to [Mo(CNBU(t))3{eta2-C(Me) = NBu(t)}(eta5-7,8-C2B9H11)][SO3CF3] (10). The structure of 10 has been determined by X-ray diffraction. Crystals are monoclinic, space group C2/c (No. 15) with a = 41.569(4) angstrom, b = 9.465(2) angstrom, c = 20.381(2) angstrom, beta = 105.616(7)-degrees, and Z = 8. The molybdenum atom is coordinated by a nido-C2B9H11 cage, three isocyanide molecules (Mo-CNBu(t) average 2.11 angstrom), and an eta2-C(Me) = NBu(t) moiety [Mo-C = 2.10(1) angstrom, mo-N = 2.14(1) angstrom]. In addition to the X-ray crystal structure determinations, the IR and NMR data for the new complexes are reported and discussed in relation to their structures.

  DOI：

  10.1021/om00015a016