bis(η5-2,4-dimethylpentadienyl)(triethylphosphine)niobium | 97551-49-0

• 英文名称: bis(η5-2,4-dimethylpentadienyl)(triethylphosphine)niobium
• CAS: 97551-49-0
• 化学式: C₂₀H₃₇NbP
• 分子量: 401.394
• InChiKey: PQVAJSURFIVNEA-SVHDLYHKSA-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：

  bis(η5-2,4-dimethylpentadienyl)(triethylphosphine)niobium 在 CO 作用下， 以 四氢呋喃 为溶剂， 以69%的产率得到
  参考文献：
  名称：

  一氧化碳与Nb（2,4-C7H11）2的膦加合物的反应：铌（I）配合物的自发还原

  摘要：

  The reactions of 17 electron Nb(2,4-C7H11)2(L) species (L = PEt3, PMe2C6H5) with CO lead to the loss of one pentadienyl ligand and formation of the 18 electron Nb(I) complexes Nb(2,4-C7H11)(L)(CO)3 in high yield. One carbonyl ligand may be thermally replaced by a second equivalent of phosphine, yielding ''trans''-Nb(2,4-C7H11)(PMe2Ph)2(CO)2, which adopts something close to a piano-stool geometry with the phosphines located by the open dienyl edge and the central dienyl carbon atom. The Nb(2,4-C7H11)(L)(CO)3. complexes are also susceptible to reduction by alkali metals, presumably leading to Nb(2,4-C7H11)(CO)32-. Oxidation of these species under CO leads to Nb(2,4-C7H11)(CO)4. Structural determinations have been carried out for Nb(2,4-C7H11)(PMe2Ph)(CO)3 and Nb(2,4-C7H11)(PMe2Ph)2(CO)2. For the former the space group is P1 with a = 7.911(5) angstrom, b = 10.490(6) angstrom, c = 12.829(6) angstrom, alpha = 105.61(4)degrees, beta = 95.88(4)degrees, gamma = 107.59(4)degrees, and V = 957.5(8) angstrom3 for Z = 2. The structure has been refined to discrepancy indices of R = 0.031 and R(w) = 0.034. For the latter the space group is P2(1)/c with a = 11.778(2) angstrom, b = 13.966(2) angstrom, c = 15.930(3) angstrom, beta = 96.33(1)degrees for Z = 4. The structure was refined to discrepancy indices of R = 0.037 and R(w) = 0.039.

  DOI：

  10.1021/om00034a060
• 作为产物：
  描述：

  Niobium, tetrachlorobis(triethylphosphine)- 、 2,4-dimethylpentadienyl (1-) 以 四氢呋喃 为溶剂， 以>45的产率得到bis(η5-2,4-dimethylpentadienyl)(triethylphosphine)niobium
  参考文献：
  名称：

  锆、铌和钼的戊二烯基化合物：“U”与“S”.eta.5-2,4-二甲基戊二烯基配位

  摘要：

  Determination des structure des complexes M(2,4-C 7 H 11 ) 2 (P(C 2 H 5 ) 3 ) avec M=Zr, Nb et Mo

  DOI：

  10.1021/ja00303a044

文献信息

• Phosphine adducts of the open metallocenes of zirconium, hafnium, niobium, and molybdenum: syntheses, structures, and reactions with carbon monoxide
  作者：Thomas E. Waldman、Lothar Stahl、David R. Wilson、Atta M. Arif、John P. Hutchinson、Richard D. Ernst

  DOI：10.1021/om00029a012

  日期：1993.5

  The reactions of MCl4(PEt3)2 complexes (M = Zr, Hf, Nb, Mo) with 4 equiv of K(2,4-C7H11) lead to the formation of M(2,4-C7H11)2PEt3 Complexes. Other related phosphine adducts may be prepared similarly, while phosphite complexes may be prepared by ligand substitution reactions. For the zirconium phosphine complex, exposure to CO generates both the monocarbonyl and the dicarbonyl complexes. Structural data have been obtained for three of the M(2,4-C7H11)2PEt3 complexes (M = Zr, Nb, Mo), as well as for Zr(2,4-C7H11)2(CO)n (n = 1, 2). The M(2,4-C7H11)2PEt3 complexes for M = Zr and Nb are isomorphous, adopting space group P1BAR with Z = 2 and respective cell constants of a = 7.988(4) angstrom, b = 8.631(4) angstrom, c = 15.649(7) angstrom, a = 87.98(4)-degrees, beta = 103.46(4)-degrees, gamma = 91.70(4)-degrees, and V = 1048.3(8) angstrom3, and a = 7.936(2) angstrom, b = 8.735(2) A, c = 15.511(5) A, a = 87.82(2)-degrees, beta = 103.79(2)-degrees, gamma = 92.12(2)-degrees, and V = 1043.0(5) A3. Crystals of the molybdenum complex are orthorhombic, belonging to space group Pbca with a = 11.244(2) angstrom, b = 14.516(2) angstrom, c = 24.963(4) angstrom, and V = 4074.5(11) angstrom3 for Z = 8. Crystals of the zirconium monocarbonyl complex are also orthorhombic, adopting space group P2(1)2(1)2(1), with a = 11.827(2) angstrom, b = 12.158(2) angstrom, c = 10.328(2) angstrom, and V = 1485.1 angstrom3 for Z = 4. Crystals of the dicarbonyl are triclinic, space group P1BAR, with a = 8.552(3) angstrom, b = 9.243(3) angstrom, c = 20.419(8) angstrom, alpha = 93.34(3)-degrees, beta = 83.88(3)-degrees, gamma = 87.97(3)-degrees, and V = 1600.7 angstrom3 for Z = 4 (two independent molecules). Except for the molybdenum complex, all mono(ligand) adducts possess the expected syn-eclipsed oriented dienyl ligands. The molybdenum complex is unusual, having one eta5-S (S = sickle) bound dienyl ligand, while the zirconium dicarbonyl has an unsymmetric orientation of tWo eta5-U bound ligands, with one carbonyl by the open edge of one dienyl ligand, the other carbonyl being by the backside of the other dienyl ligand.