Ta(CO)2(1,2-bis(diethylphosphino)ethane)2Cl | 143123-81-3

• 英文名称: Ta(CO)2(1,2-bis(diethylphosphino)ethane)2Cl
• 英文别名: {Ta(CO)2(depe)2Cl}
• CAS: 143123-81-3
• 化学式: C₂₂H₄₈ClO₂P₄Ta
• 分子量: 684.918
• InChiKey: DRLXUHLUIHYECF-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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

• 作为反应物：
  描述：

  Ta(CO)2(1,2-bis(diethylphosphino)ethane)2Cl 、 1,2-双(氯二甲基硅基)乙烷 在 40percent Na/Hg 作用下， 以 四氢呋喃 为溶剂， 以75%的产率得到Ta(Me2Si(CH2)OCCO(CH2)SiMe2)(1,2-bis(diethylphosphino)ethane)Cl
  参考文献：
  名称：

  5二羰基到二甲氧乙炔配合物的还原偶联：环形成和增加的立体需求的影响。

  摘要：

  Convenient syntheses of dicarbonyl complexes of the type [M(CO)(2)(depe)(2)Cl] (depe = 1,2-bis(diethylphosphino)ethane, M = Ta (1), Nb (3)) and [M(CO)(2)(dbpe)(2)Cl] (dbpe = 1,2-bis(dibutylphosphino)ethane, M = Ta (2), Nb (4)) having increased steric demands at the high coordinate metal centers are described. Reductive coupling of the CO ligands of 1-4 occurs to provide products of the type [M(R'3SiOC double bond COSiR'(3))(R(2)PCH(2)CH(2)PR(2))(2)]X. Single crystal X-ray structural studies were carried out for two reductively coupled products prepared with 1,2-bis(chlorodimethylsilyl)ethane as the electrophile, [V(Me(2)SiOC double bond COSiMe(2))(dmpe)(2)Cl] (monoclinic, space group C2/c, a = 9.349(2) Angstrom, b = 20.548(3) Angstrom, c = 16.146(4) Angstrom, beta = 104.79(1)degrees, and V = 2999(1) Angstrom(3)) and [Ta(Me(2)SiOC double bond COSiMe(2))(depe)(2)Cl] (monoclinic, space group Cc, a = 11.512(1) Angstrom, b = 18.311(3) Angstrom, c 18.493(3) Angstrom, beta = 97.322(7)degrees, and V = 3875(1) Angstrom(3)). In these complexes, the acetylene is contained within a newly formed eight-membered ring, and the ligands are arranged in a pentagonal bipyramid geometry comprising two axial phosphorus atoms and five equatorial ligands, the coupled carbons, a trans chloride, and the remaining two phosphorus atoms.

  DOI：

  10.1021/om00003a044
• 作为产物：
  描述：

  1,2-双(二乙基磷)乙烷 、 五氯化钽 在 Na/Hg; 、 HgCl₂ 、 catalyst: magnesium anthracenide 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 以37%的产率得到Ta(CO)2(1,2-bis(diethylphosphino)ethane)2Cl
  参考文献：
  名称：

  Protasiewicz, John D.; Bianconi, Patricia A.; Williams, Ian D., Inorganic Chemistry, 1992, vol. 31, # 20, p. 4134 - 4142

  摘要：

  DOI：

文献信息

• Reactions of Low-Valent Group V Dicarbonyl Phosphine Complexes with Carbon-Based Electrophiles To Produce Metal Alkyl, Acyl, Carbyne, and Acetylene Complexes
  作者：Brian S. Bronk、John D. Protasiewicz、Laura E. Pence、Stephen J. Lippard

  DOI：10.1021/om00005a018

  日期：1995.5

  The [V(CO)(2)(dmpe)(2)](-) anion reacts with Et(3)OBF(4) and EtOTf to afford the unexpected product of formal C-alkylation, [V(eta(2)-C(O)Et)(CO)(dmpe)(2)], which has been structurally characterized by X-ray crystallography (space group Pna2(1), a = 12.917(2) Angstrom, b = 12.335(2) Angstrom c = 14.331(2) Angstrom, V = 2283.4(5) Angstrom(3)). The formation of species derived by O-acylation of the CO ligands in the [Ta(CO)(2)(dmpe)(2)](-) and [Ta(CO)(2)(depe)(2)](-) anions was indirectly established by isolation and characterization of products in which two CO ligands had coupled to form acetylene complexes. Addition of 2 equiv of acetyl chloride to Na[Ta(CO)(2)(dmpe)(2)] or Na[Ta(CO)(2)(depe)(2)] yielded the acetylene complexes [Ta(AcOC=COAc)(dmpe or depe)(2)Cl]. The structure of the dmpe derivative was confirmed in a single-crystal X-ray determination (space group C2, a = 14.964(2) Angstrom, b = 11.960(2) Angstrom, c = 31.710(5) Angstrom, beta = 102.77(1)degrees, V = 5535(1) Angstrom(3)). Additional proof of direct alkylation at terminal CO ligands was provided by isolation of mixed siloxy/alkoxyacetylene coupled products [M(R(3)(')SiOC=COR)(dmpe)(2)X] (R = Et, Ac, CO(2)Me; R'Si-3 = (t)BuPh(2)Si, (Pr3Si)-Pr-i) and [M(R'3SiOC=COR)(depe)(2)X] (R = Et, Ac; R'Si-3 = (t)BuPh(2)Si, (Pr3Si)-Pr-i, Me(3)Si) from reactions of the siloxycarbyne precursors [M(COSiR'(3))-(CO)(dmpe)(2)] and [M(COSiR'(3))(CO)(depe)(2)] (M = Nb, Ta) with carbon-based electrophiles. The proper choice of carbon-based electrophile and reaction conditions is crucial in order to avoid oxidation of these low-valent metal complexes to [M(CO)(2)(dmpe)(2)X], which can occur competitively or exclusively.