| 189446-53-5

• CAS: 189446-53-5；189518-64-7；189518-63-6
• 化学式: C₁₂H₃₄Cl₄N₂P₂W₂
• 分子量: 777.875
• InChiKey: TZBZWWWQSSDYAM-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
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• 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

• 作为产物：
  描述：

  正丙胺 、 四氯化钨 、 三甲基膦 在 Na-amalgam 、 THF 作用下， 以 四氢呋喃 为溶剂， 以42%的产率得到
  参考文献：
  名称：

  W₂Cl₄(NR₂)₂(PR‘₃)₂ Molecules. 8. Synthesis and Structural Characterization of Both Cis Isomers of Stoichiometry W₂Cl₄(NHR)₂(PMe₃)₂, R = Et, Prⁿ, and Buⁿ. Direct Evidence Favoring an Internal Flip Mechanism for Cis−Trans Isomerization

  摘要：

  The triply-bonded ditungsten(III) complexes of stoichiometry W2Cl4(NHR)(2)(PMe3)(2) (R=Et, Pr-n, Bu-n) are formed by a two-step, one-pot, synthesis from the reaction of W2Cl6(THF)(4) with the appropriate alkylamines NH2R(R=Et, Pr-n, Bu-n), followed by phosphine substitution. The dinuclear species W2Cl4(NHR)(2)(NH2R)(2) are the probable intermediate complexes for such reactions. In each case, three isomeric forms have been detected in solution by P-31{H-1})NMR spectroscopy, and they are formulated as the trans isomers and the two types of cis isomers possessing C-i and C-2 symmetries. It has also been shown that the trans isomers are the initial (kinetic) products irrespective of the R group. The X-ray crystallographic characterization of the C-i isomer of cis-W2Cl4(NHEt)(2)(PMe3)(2) (1), the C-2 isomer of cis-W2Cl4(NHPrn)(2)(PMe3)(2) (2), and the C-2 isomer of cis-W2Cl4(NHBun)(2)(PMe3)(2) (3a,b) has been accomplished. Crystallographic data are as follows: compound 1, triclinic space group P (1) over bar, a = 7.4366(2) Angstrom, b = 8.8618(6) Angstrom, c = 9.352(1) Angstrom, alpha = 105.262(6)degrees, beta = 109.20(1)degrees, gamma = 94.423(9)degrees, Z = 1; compound 2, monoclinic space group 12/a, a = 13.1268(8) Angstrom, b = 10.871(1) Angstrom, c = 17.106(1) Angstrom, beta = 92.872(5)degrees, Z = 4; compound 3a, monoclinic space group P2(1)/c, a = 22.058(9) Angstrom, b = 8.562(1) Angstrom, c = 29.768(8) Angstrom, beta 105.642(1)degrees, Z = 8; compound 3b, P2(1)/n, a = 8.5429(8) Angstrom, b = 18.393(2) Angstrom, c = -16.957(3) Angstrom, beta 90.264(5)degrees, Z = 4. Complex 1 is the first structurally characterized compound with a W2Cl4N2P2 core of C-i symmetry. The midpoint of the W-W unit in 1 resides on an inversion center and compound 1 is therefore nonchiral. For 2 and 3 (3a,b), the molecules are chiral since each has only C-2 symmetry. The W-W distances for 1, 2, 3a, and 3b are 2.3066(6), 2.3170(6), 2.3162(9), and 2.3147(5) Angstrom, respectively. In these molecules there are two intramolecular hydrogen bonds across the W-W triple bond, thus ensuring an essentially eclipsed geometry in each case. Each of them has the P and N atoms on each W atom cis to each other. The observation and, in one case, 1, the isolation of the unprecedented cis isomers of C-i symmetry provide support for our earlier proposal that the isomerization processes occur by an ''internal flip'' of the W-2 unit within the quasi-cubic set of coordinated ligand atoms.

  DOI：

  10.1021/ic9700361