Chlororhenium;2-isocyano-2-methylpropane;tricyclohexylphosphane | 183674-84-2

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: Chlororhenium;2-isocyano-2-methylpropane;tricyclohexylphosphane
• CAS: 183674-84-2
• 化学式: C₅₁H₉₃ClN₃P₂Re
• 分子量: 1031.93
• InChiKey: BSXGHJDQGLFDHB-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  18.73
• 重原子数：
  58
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  13.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Chlororhenium;2-isocyano-2-methylpropane;tricyclohexylphosphane 、 二氯甲烷 以 二氯甲烷 为溶剂， 生成 Re(CNC(CH₃)3)3(P(C₆H₁₁)3)2Cl⁽¹⁺⁾*Cl^(1-)*3CH₂Cl₂=[Re(CNC(CH₃)3)3(P(C₆H₁₁)3)2Cl]Cl*3CH₂Cl₂
  参考文献：
  名称：

  Rhenium Dihydrogen Complexes with Isonitrile Coligands:  Novel Displacement of Chloride by Hydrogen

  摘要：

  The syntheses, properties, and characterization of several new complexes, Re(CNtBu)(3)(PCy(3))(2)H (1a), Re(CNtBu)(3)(PR(3))(2)Cl [R = Cy, Ph (2a, 2b)], the 17-electron [Re(CNtBu)(3)(PCy(3))(2)Cl](+) (3a), the dihydrogen complex, [Re(CNtBu)(3)(PR(3))(2)(H-2)](+) [R = Cy, Ph (4a, 4b)], the coordinatively unsaturated [Re(CNtBu)(3)(PCy(3))(2)](+) (5a), and [Re(CNtBu)(4)(PCy(3))(2)](+) (6a) are reported. In addition, spectroscopic evidence for the dinitrogen complex [Re(CNtBu)(3)-(PCy(3))(2)(N-2)](+), and the dihydrogen complex [Re(CNtBu)(5)(H-2)](+) is presented. Thermodynamic parameters have been obtained for the equilibrium system, Re(CNtBu)(3)(PCy(3))(2)Cl (2a) + H-2 reversible arrow [Re(CNtBu)(3)(PCy(3))(2)(H-2)]Cl (4a). H-1 and P-31{H-1} NMR studies (CD2Cl2) over the temperature range 286-316 K afford values of Delta H degrees = -18.0 +/- 0.7 kcal/mol, Delta S degrees = -44 +/- 2 eu, and Delta G degrees(298) = -4.8 +/- 1.3 kcal/mol for this equilibrium. The complexes 4a and 4b are characterized as dihydrogen complexes. Their J(HD) (R = Cy, 30.3 Hz; R = Ph, 30.9 Hz) and T-l(min) values of 8 ms (300 MHz) are consistent with H-H distances of ca. 0.80 Angstrom. [Re(CNtBu)(5)(HD)](+) is also characterized as a dihydrogen complex based on a J(HD) of 33.4 Hz. This complex could not be isolated at room temperature, even with noncoordinating counteranions, due to the lability of the H-2 ligand. [Re(PMe(3))(5)HD](+) shows no H-D coupling and is characterized as a dihydride complex. The unsaturated complex [Re(CNtBu)(3)(PCy(3))(2)](+) (5a) is found to undergo a dynamic isonitrile rearrangement on the NMR time scale. H-1 NMR spin saturation transfer studies over a temperature range of 254-297 K afford the activation parameters Delta H double dagger = 11.4 +/- 0.8 kcal/mol, Delta S double dagger = -17.6 +/- 1.6 eu, and Delta G double dagger(298) = 16.6 +/- 1.2 kcal/mol. The molecular structures of 2a and 3a have been determined by X-ray crystallography. 2a shows an unusually long Re-Cl bond distance of 2.596(2) Angstrom.

  DOI：

  10.1021/ja961994p
• 作为产物：
  描述：

  盐酸 、 2-isocyano-2-methylpropane;rhenium monohydride;tricyclohexylphosphane 以 乙醚 为溶剂， 以21%的产率得到Chlororhenium;2-isocyano-2-methylpropane;tricyclohexylphosphane
  参考文献：
  名称：

  Rhenium Dihydrogen Complexes with Isonitrile Coligands:  Novel Displacement of Chloride by Hydrogen

  摘要：

  The syntheses, properties, and characterization of several new complexes, Re(CNtBu)(3)(PCy(3))(2)H (1a), Re(CNtBu)(3)(PR(3))(2)Cl [R = Cy, Ph (2a, 2b)], the 17-electron [Re(CNtBu)(3)(PCy(3))(2)Cl](+) (3a), the dihydrogen complex, [Re(CNtBu)(3)(PR(3))(2)(H-2)](+) [R = Cy, Ph (4a, 4b)], the coordinatively unsaturated [Re(CNtBu)(3)(PCy(3))(2)](+) (5a), and [Re(CNtBu)(4)(PCy(3))(2)](+) (6a) are reported. In addition, spectroscopic evidence for the dinitrogen complex [Re(CNtBu)(3)-(PCy(3))(2)(N-2)](+), and the dihydrogen complex [Re(CNtBu)(5)(H-2)](+) is presented. Thermodynamic parameters have been obtained for the equilibrium system, Re(CNtBu)(3)(PCy(3))(2)Cl (2a) + H-2 reversible arrow [Re(CNtBu)(3)(PCy(3))(2)(H-2)]Cl (4a). H-1 and P-31{H-1} NMR studies (CD2Cl2) over the temperature range 286-316 K afford values of Delta H degrees = -18.0 +/- 0.7 kcal/mol, Delta S degrees = -44 +/- 2 eu, and Delta G degrees(298) = -4.8 +/- 1.3 kcal/mol for this equilibrium. The complexes 4a and 4b are characterized as dihydrogen complexes. Their J(HD) (R = Cy, 30.3 Hz; R = Ph, 30.9 Hz) and T-l(min) values of 8 ms (300 MHz) are consistent with H-H distances of ca. 0.80 Angstrom. [Re(CNtBu)(5)(HD)](+) is also characterized as a dihydrogen complex based on a J(HD) of 33.4 Hz. This complex could not be isolated at room temperature, even with noncoordinating counteranions, due to the lability of the H-2 ligand. [Re(PMe(3))(5)HD](+) shows no H-D coupling and is characterized as a dihydride complex. The unsaturated complex [Re(CNtBu)(3)(PCy(3))(2)](+) (5a) is found to undergo a dynamic isonitrile rearrangement on the NMR time scale. H-1 NMR spin saturation transfer studies over a temperature range of 254-297 K afford the activation parameters Delta H double dagger = 11.4 +/- 0.8 kcal/mol, Delta S double dagger = -17.6 +/- 1.6 eu, and Delta G double dagger(298) = 16.6 +/- 1.2 kcal/mol. The molecular structures of 2a and 3a have been determined by X-ray crystallography. 2a shows an unusually long Re-Cl bond distance of 2.596(2) Angstrom.

  DOI：

  10.1021/ja961994p