NbCl(CO)2(dmpe)2 | 66507-17-3

• 英文名称: NbCl(CO)2(dmpe)2
• CAS: 66507-17-3
• 化学式: C₁₄H₃₂ClNbO₂P₄
• 分子量: 484.661
• InChiKey: BOHIIQBWWGTABS-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：

  NbCl(CO)2(dmpe)2 在 Na/Hg 、 (i-Pr)3SiCl 作用下， 以 四氢呋喃 为溶剂， 以94%的产率得到
  参考文献：
  名称：

  由羰基金属和异氰化物配合物生成的卡宾；羰基和 CNR 配体还原偶联的中间体

  摘要：

  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] +

  DOI：

  10.1021/ja00216a062
• 作为产物：
  描述：

  四氯双(四氢呋喃)合铌(IV) 、 1,2-双(二甲基瞵)乙烷 、 一氧化碳 在 Mg 作用下， 以 四氢呋喃 为溶剂， 以80%的产率得到NbCl(CO)2(dmpe)2
  参考文献：
  名称：

  铌和钽的羰基配合物和铌二氮配合物的证据：羰基二氯环戊二烯基双（二甲基苯基膦）钽的结构

  摘要：

  [M（η-C的反应的5 ħ 5）氯4 ]与叔膦等配体和还原下碳的产品（M = Nb或Ta）的一氧化碳给予羰基如[M（η-C 5 H ^ 5）（CO）Cl 2（PR 3）2 ]（PR 3 =叔膦），但没有N 2类似物。的晶体和分子结构[TA（η-C 5 H ^ 5）（CO）氯2（PME 2 PH）2 ]已被重原子方法，使用钼确定ķ α辐射和1 591个非零反射。该空间群是六边形P 6 5，a = 13.661（2），c = 26.420（11）Å，Z =6。在收敛时，R = 0.035 7和R '= 0.037 0。通过在CO下还原可容易地获得Nb（CO）2 Cl（Me 2 PCH 2 CH 2 PMe 2）2 ]，并且还描述了制备不纯的二氮配合物，该配合物与酸产生一些肼。

  DOI：

  10.1039/dt9810000793

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.
• Mechanistic studies of the reductive coupling of carbon monoxide in seven-coordinate niobium(I) and tantalum(I) dicarbonyl complexes
  作者：Raymond N. Vrtis、Shuncheng Liu、C. Pulla Rao、Simon G. Bott、Stephen J. Lippard

  DOI：10.1021/om00047a061

  日期：1991.1

  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, [TaMe3SiOC = 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 [Taeta2-(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.
• 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：——
• Reductive coupling of carbon monoxide with methyl isocyanide in a seven-coordinate niobium complex
  作者：Edmund M. Carnahan、Stephen J. Lippard

  DOI：10.1021/ja00164a064

  日期：1990.4