trans-(PhC*C-)2-tetrakis(triethyl phosphite)ruthenium(II) | 168062-81-5

• 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: trans-(PhC*C-)2-tetrakis(triethyl phosphite)ruthenium(II)
• 英文别名: ethynylbenzene;ruthenium(2+);triethyl phosphite
• CAS: 168062-81-5
• 化学式: C₄₀H₇₀O₁₂P₄Ru
• 分子量: 967.954
• InChiKey: GLCJPSMFMCQHQJ-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：

  trans-(PhC*C-)2-tetrakis(triethyl phosphite)ruthenium(II) 、 2,4-二硝基苯硫氯 以 乙醚 为溶剂， 以55%的产率得到trans-[(PhC*C-)(Ph(2,4-(NO2)2-C6H3S-)C=C=)-tetrakis(triethyl phosphite)ruthenium(II)]Cl
  参考文献：
  名称：

  亚磷酸酯配体稳定的新型双（乙炔）和乙酰内酯-亚乙烯基钌（II）配合物的制备，结构和反应性

  摘要：

  Bis(alkynyl) complexes Ru(C=CR)(2)P-4 (1-3) (R = Ph, p-tolyl, (t)Bu; P = P(OMe)(3) (1), P(OEt)(3) (2), PPh(OEt)(2) (3)) were prepared by reacting RuCl2P4 with excess Li+ RC=C-, and a trans geometry was established both in solids (X-ray) and in solution. The reaction of these alkynyls (1-3) with electrophilic reagent depends on the nature of the phosphite ligand. Vinylidene-acetylide derivatives [Ru(C=CR){=C=C(R(1))R}P-4](+) (R(1) = H (4, 5), CH3 (7, 8), ArN=N (10), I (12), 2,3-(NO2)(2)C6H3S (14)) were prepared with P(OMe)(3) and P(OEt)(3) ligand by treatment of 1 and 2 with HBF4, CF(3)SO(3)Me, ArN2+BF4-, I-2, and 2,3-(NO2)(2)C6H3SCl, respectively. Instead, only the diazo- and iodovinylidenes [Ru(C=CR){=C=C(R(1))R}P-4](+) (R(1) = p-tolN=N (11), I (13)) were obtained with the PPh(OEt)(2) phosphite ligand. These vinylidene compounds were fully characterized by IR, H-1, P-31, and C-13 NMR spectra, and a single-crystal X-ray structure determination of complex [Ru(C=CPh){=C=C(Me)Ph)-{P(OEt)(3)}(4)]CF3SO3 (8a) is reported. The alkynyl-vinylidene [Ru(C=CR){=C=C(H)R}P-4](+) cations (4, 5) rearrange in solution to enynyl [Ru(eta(3)-RC(3)CHR)P-4](+) derivatives, and the reaction is inhibited by the presence of free alkyne. Kinetic data support a mechanism involving a pentacoordinate intermediate formed by loss of the vinylidene ligand. Substitution of the =C=C(H)R ligand by phosphite, isocyanide, and nitrile is easy in 4 and 5 and leads to [Ru(C=CPh){P(OMe)(3)}P-4](+) (17), [Ru(C=CPh)(p-tolNC)P-4](+) (18), and [Ru(p-tolCN)(2)P-4](2+) (19) (P = P(OEt)(3)), derivatives. Deprotonation with a base of the vinylidene ligand in 4 and 5, giving Ru(C=CR)(2)P-4, was also detected.

  DOI：

  10.1021/om00009a015
• 作为产物：
  描述：

  trans-[(PhC*C-)(PhCH=C=)-tetrakis(triethyl phosphite)ruthenium(II)](tetrafluoroborate) 在 LiCl, LiBr 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 以20%的产率得到trans-(PhC*C-)2-tetrakis(triethyl phosphite)ruthenium(II)
  参考文献：
  名称：

  亚磷酸酯配体稳定的新型双（乙炔）和乙酰内酯-亚乙烯基钌（II）配合物的制备，结构和反应性

  摘要：

  Bis(alkynyl) complexes Ru(C=CR)(2)P-4 (1-3) (R = Ph, p-tolyl, (t)Bu; P = P(OMe)(3) (1), P(OEt)(3) (2), PPh(OEt)(2) (3)) were prepared by reacting RuCl2P4 with excess Li+ RC=C-, and a trans geometry was established both in solids (X-ray) and in solution. The reaction of these alkynyls (1-3) with electrophilic reagent depends on the nature of the phosphite ligand. Vinylidene-acetylide derivatives [Ru(C=CR){=C=C(R(1))R}P-4](+) (R(1) = H (4, 5), CH3 (7, 8), ArN=N (10), I (12), 2,3-(NO2)(2)C6H3S (14)) were prepared with P(OMe)(3) and P(OEt)(3) ligand by treatment of 1 and 2 with HBF4, CF(3)SO(3)Me, ArN2+BF4-, I-2, and 2,3-(NO2)(2)C6H3SCl, respectively. Instead, only the diazo- and iodovinylidenes [Ru(C=CR){=C=C(R(1))R}P-4](+) (R(1) = p-tolN=N (11), I (13)) were obtained with the PPh(OEt)(2) phosphite ligand. These vinylidene compounds were fully characterized by IR, H-1, P-31, and C-13 NMR spectra, and a single-crystal X-ray structure determination of complex [Ru(C=CPh){=C=C(Me)Ph)-{P(OEt)(3)}(4)]CF3SO3 (8a) is reported. The alkynyl-vinylidene [Ru(C=CR){=C=C(H)R}P-4](+) cations (4, 5) rearrange in solution to enynyl [Ru(eta(3)-RC(3)CHR)P-4](+) derivatives, and the reaction is inhibited by the presence of free alkyne. Kinetic data support a mechanism involving a pentacoordinate intermediate formed by loss of the vinylidene ligand. Substitution of the =C=C(H)R ligand by phosphite, isocyanide, and nitrile is easy in 4 and 5 and leads to [Ru(C=CPh){P(OMe)(3)}P-4](+) (17), [Ru(C=CPh)(p-tolNC)P-4](+) (18), and [Ru(p-tolCN)(2)P-4](2+) (19) (P = P(OEt)(3)), derivatives. Deprotonation with a base of the vinylidene ligand in 4 and 5, giving Ru(C=CR)(2)P-4, was also detected.

  DOI：

  10.1021/om00009a015

文献信息

• Syntheses and molecular structures of trans-bis(alkynyl) tetrakis-triethylphosphite ruthenium complexes
  作者：Samantha G. Eaves、Brian W. Skelton、Paul J. Low

  DOI：10.1016/j.jorganchem.2017.04.028

  日期：2017.10

  A simple synthesis of complexes trans-[Ru(C≡CC6H4-4-R)2P(OEt)3}4] from trans-[RuCl2P(OEt)3}4] and the terminal alkyne is described. Crystallographically determined molecular structures indicate a range of conformers, with the ethynyl arylene rings differing in their orientation with respect to each other across the RuP(OEt)3}4 fragment. Electrochemical analysis reveals a well-behaved one-electron

  复合物的简单的合成反式的[Ru（C≡CC 6 ħ 4 -4-R）2 P（OET）3 } 4 ]从反式-将[RuCl 2 P（OET）3 } 4 ]与末端炔描述。晶体学确定的分子结构指示一系列构象异构体，其中乙炔基亚芳基环在整个Ru P（OEt）3 } 4片段上彼此之间的取向不同。电化学分析揭示了一个表现良好的单电子氧化过程，这是只有约100 mV的更积极的是，类似的反式的[Ru（C≡CC 6H 4 -4-R）2（dppe）2 ]络合物。量子化学计算揭示了很大程度上离域的电子结构，并表明这些化合物可能在单分子电子学中用作线状分子。