{Ta(CO)2(dmpe)2Cl} | 61916-36-7

• 英文名称: {Ta(CO)2(dmpe)2Cl}
• CAS: 61916-36-7
• 化学式: C₁₄H₃₂ClO₂P₄Ta
• 分子量: 572.703
• InChiKey: ZBKBHEHECMYIOE-UHFFFAOYSA-M

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：

  {Ta(CO)2(dmpe)2Cl} 在 sodium amalgam 作用下， 以 四氢呋喃 为溶剂， 以92%的产率得到
  参考文献：
  名称：

  一氧化碳在七配位铌（I）和钽（I）二羰基络合物中还原偶联的机理研究

  摘要：

  The mechanism by which the two carbonyl ligands in the seven-coordinate complexes [M(CO)2(dmpe)2Cl] [M = Ta, Nb; dmpe = 1,2-bis(dimethylphosphino)ethane] are reductively coupled has been elucidated. The first step involves two-electron reduction to afford the [M(CO)2(dmpe)2]- anion, the tantalum analogue of which was structurally characterized as the tetra-hexylammonium salt. The geometry of this anion is distorted octahedral with cis-carbonyl ligands. Reaction of the anion with 1 equiv of trialkylsilyl chloride yields the siloxycarbyne species [M(= COSiR3)(CO)(dmpe)2] (M = Ta or Nb), formed by electrophilic attack of the silyl halide on the carbonyl oxygen atom. The tantalum triisopropylsiloxycarbyne complex, the X-ray structural analysis of which is described, reacts with 1 equiv of trimethylsilyl chloride to afford the asymmetric acetylene complex, [Ta{Me3SiOC = COSi(iota-Pr)3}(dmpe)2Cl], which was also structurally characterized. The transition state between the carbyne and coupled products may be an eta2-ketenyl of the type [Ta{eta2-(O)CCOSiR3}(dmpe)2X]- (X = halide). Such an assignment is supported by a series of experiments involving addition of different silyl halide reagents (Me3SiX; X = Cl, I, OTf) to (n-C6H13)4N[Ta(CO)2(dmpe)2]. The generality of the reaction mechanism is discussed.

  DOI：

  10.1021/om00047a061
• 作为产物：
  描述：

  、 {Ta(Me3SiOCCOSiMe3)(dmpe)2Cl} 在 Al₂O₃ 作用下， 以 四氢呋喃 为溶剂， 生成 {Ta(CO)2(dmpe)2Cl}
  参考文献：
  名称：

  两个一氧化碳配体还原偶联形成配位炔

  摘要：

  Etude du couplage reducteur de CO 浇注前 une nouvelle espece de produit Derive de CO, Me 3 SiOC≡COSiMe 3 稳定标准配位 a Ta。结构分子 obtenu: [Ta(Me 3 SiOC≡COSiMe 3 )(dmpe) 2 Cl]

  DOI：

  10.1021/ja00262a030

文献信息

• Mono-η-cyclopentadienylniobium chemistry: ternary phosphine, carbonyl, 3,4-dimethylhexa-2,4-diene, halogeno-, and hydrido-derivatives
  作者：Mark J. Bunker、Malcolm L. H. Green

  DOI：10.1039/dt9810000085

  日期：——

  The new compounds [Nb(η-C5H5)(dmpe)(CO)2], [Nb(η-C5H5)(dmpe)(CO)X2], X = Cl, Br, or I, [Nb(η-C5H5)(dmpe)2], [Nb(η-C5H5)(dmpe)(CO)2H][PF6], [Nb(η-C5H5)(dmpe)H (µ-H)}2], [Nb(η-C5H5)(dmpe)H(µ-H2BH2)], and [Nb(η-C5H5)(dmpe) Cl][PF6][dmpe = 1,2-bis(dimethylphosphino)ethane] are described. Sodium amalgam reduction of [Nb(η-C5H5)(dmpe)(CO)Cl2] in the presence of but-2-yne followed by addition of hydrogen

  新化合物[铌（η-C 5 H ^ 5）（DMPE）（CO）2 ]，[Nb的（η-C 5 H ^ 5）（DMPE）（CO）X 2 ]，X =氯，溴，或我[铌（η-C 5 H ^ 5）（DMPE）2 ]，[Nb的（η-C 5 H ^ 5）（DMPE）（CO）2 H] [PF 6 ]，[铌（η-C 5 H ^ 5）（DMPE）H（μ-H）} 2 ]，[Nb的（η-C 5 H ^ 5）（DMPE）H（μ-H 2 BH 2）]和[Nb的（η-C 5 H ^ 5） （DMPe）Cl] [PF 6描述了[DMPe ＝ 1，2-双（二甲基膦基）乙烷]。钠汞齐还原的[铌（η-C 5 H ^ 5）（DMPE）（CO）氯2 ]在丁-2-炔的存在下，随后加入氯化氢给出[铌（η-C 5 H ^ 5）（ c ^ 4 ħ 2我4）]和另外的还原，得到[铌（η-C 5 H ^ 5）（η-C 4 H ^ 2我4）（μ-Cl）的}
• Carbynes generated from metal carbonyl and isocyanide complexes; intermediates in the reductive coupling of carbonyl and CNR ligands
  作者：Raymond N. Vrtis、C. Pulla. Rao、Steve. Warner、Stephen J. Lippard

  DOI：10.1021/ja00216a062

  日期：1988.4

  Isolement et caracterisation structurale d'un intermediaire-cle dans le couplage reductif de CO, [M(CO)COSi(i-Pr) 3 }(dmpe) 2 ] (M=Nb, Ta). On prepare egalement [Re(CNHR)(CNR) 2 (PMePh 2 ) 2 Cl] +

  Isolement et caracterisation structuree d'un intermediaire-cle dans le couplage reductif de CO, [M(CO)COSi(i-Pr) 3 }(dmpe) 2 ] (M=Nb, Ta)。[Re(CNHR)(CNR) 2 (PMePh 2 ) 2 Cl] +
• 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.
• Bianconi, Patricia A.; Vrtis, Raymond N.; Rao, Ch. Pulla, Organometallics, 1987, vol. 6, # 9, p. 1968 - 1977
  作者：Bianconi, Patricia A.、Vrtis, Raymond N.、Rao, Ch. Pulla、Williams, Ian D.、Engeler, Mary P.、Lippard, Stephen J.

  DOI：——

  日期：——
• Carnahan, Edmund M.; Rardin, R. Lynn; Bott, Simon G., Inorganic Chemistry, 1992, vol. 31, # 25, p. 5193 - 5201
  作者：Carnahan, Edmund M.、Rardin, R. Lynn、Bott, Simon G.、Lippard, Stephen J.

  DOI：——

  日期：——