[W(dinitrogen)(acetonitrile)(dppe)2] | 66368-19-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [W(dinitrogen)(acetonitrile)(dppe)2]
• 英文别名: Acetonitrile;2-diphenylphosphanylethyl(diphenyl)phosphane;molecular nitrogen;tungsten
• CAS: 66368-19-2
• 化学式: C₅₄H₅₁N₃P₄W
• 分子量: 1049.76
• InChiKey: CEEKYKYMOXXHFX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.06
• 重原子数：
  62
• 可旋转键数：
  14
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  71.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  tetrafluoroboric acid 、 [W(dinitrogen)(acetonitrile)(dppe)2] 以 乙醚 、 苯 为溶剂， 以58%的产率得到trans-(ethylimido)fluorobis[1,2-bis(diphenylphosphino)ethane]tungsten tetrafluoroborate
  参考文献：
  名称：

  Reduction of a Coordinated Acetonitrile Ligand:  Synthesis of an Ethylimido Complex of Tungsten

  摘要：

  Treatment of the dinitrogen complex W(N-2)(2)(dppe)(2) (1; dppe = 1,2-bis(diphenylphosphino)ethane) with trifluoromethanesulfonic acid yields the novel hydrazido complex [W(N2H2)(oTf)(dppe)(2)](+)[oTf](-) (2; OTf = CF3SO3-). The triflato ligand is readily displaced by other ligands and coordinating solvents. The triflato complex 2 yields the complex [W(N2H2)(NCCH3)(dppe)(2)](2+) (5), when it is dissolved in acetonitrile, and 5 is readily deprotonated by a variety of bases to give the acetonitrile-dinitrogen complex W(N-2)(NCCH3)(dppe)(2) (3). Complex 3 is protonated at the beta-carbon by tetrafluoroboric acid, resulting in the reduction of the coordinated nitrile to give the novel imido complex [WF(NCH2CH3)(dppe)(2)](+)[BF4](-)(4). The X-ray crystal structure of the imido complex 4 reveals an effectively linear W-N-C bond (171.8 degrees) in the imido ligand with a W-N bond length of 1.741(4) Angstrom.

  DOI：

  10.1021/om970829v
• 作为产物：
  描述：

  trans-bis[1,2-bis(diphenylphosphino)ethane]hydrazido(triflato)tungsten triflate 、 乙腈 在 NaBH₄ or Et₃N or KO(t)Bu 作用下， 以 乙腈 为溶剂， 以76%的产率得到[W(dinitrogen)(acetonitrile)(dppe)2]
  参考文献：
  名称：

  Reduction of a Coordinated Acetonitrile Ligand:  Synthesis of an Ethylimido Complex of Tungsten

  摘要：

  Treatment of the dinitrogen complex W(N-2)(2)(dppe)(2) (1; dppe = 1,2-bis(diphenylphosphino)ethane) with trifluoromethanesulfonic acid yields the novel hydrazido complex [W(N2H2)(oTf)(dppe)(2)](+)[oTf](-) (2; OTf = CF3SO3-). The triflato ligand is readily displaced by other ligands and coordinating solvents. The triflato complex 2 yields the complex [W(N2H2)(NCCH3)(dppe)(2)](2+) (5), when it is dissolved in acetonitrile, and 5 is readily deprotonated by a variety of bases to give the acetonitrile-dinitrogen complex W(N-2)(NCCH3)(dppe)(2) (3). Complex 3 is protonated at the beta-carbon by tetrafluoroboric acid, resulting in the reduction of the coordinated nitrile to give the novel imido complex [WF(NCH2CH3)(dppe)(2)](+)[BF4](-)(4). The X-ray crystal structure of the imido complex 4 reveals an effectively linear W-N-C bond (171.8 degrees) in the imido ligand with a W-N bond length of 1.741(4) Angstrom.

  DOI：

  10.1021/om970829v

文献信息

• Reactivities of the coordinated organonitriles in molybdenum(0) and tungsten(0) phosphine complexes: protonation of the nitrile carbon and cleavage of the CN triple bond
  作者：Hidetake Seino、Yoshiaki Tanabe、Youichi Ishii、Masanobu Hidai

  DOI：10.1016/s0020-1693(98)00060-7

  日期：1998.10

  The molybdenum and tungsten dinitrogen-organonitrile complexes trans-[M(N2)(NCR)(dppe)2] (2, MMo; 4, MW; RPh, C6H4Me-p, C6H4OMe-p, Me; dppePh2PCH2CH2PPh2) underwent double protonation at the nitrile carbon atom with loss of N2 and a change in oxidation state to +4 on treatment with hydrochloric acid to afford the cationic imido complexes trans-[MCl(NCH2R)(dppe)2]+. The solid-state structure of

  钼和钨二氮-有机腈络合物反式-[M（N 2）（NCR）（dppe）2 ]（2，MMo; 4，MW;RPh，C 6 H 4 Me- p，C 6 ħ 4 OMe- p中，Me;dppePh 2 PCH 2 CH 2 PPH 2）行双重在与氮损失腈碳原子质子化2和氧化态到4用盐酸，得到的改变治疗阳离子亚氨基配合物反式-[MCl（NCH 2 R）（dppe）2 ] +。通过单晶X射线分析确定了反式-[WCl（NCH 2 CH 3）（dppe）2 ] [PF 6 ]·CH 2 Cl 2的固态结构。氟硼酸或氢溴酸使配合物2质子化也形成了类似的反式-[MoX（NCH 2 R）（dppe）2 ] +（XF，Br）的亚氨基配合物。相反，二氮配合物反式-[Mo（N 2）2（dppe）2]与两个当量反应。苯甲酰乙腈（具有酸性CH氢原子的腈）的合成，得到亚硝基复合物反式-[Mo（N）（NKCCHCOPh）（dppe）2
• Double deprotonation of coordinated ethylimide to CH3CN: molecular mechanism and relevance to the chemistry of Mo and W organoimides
  作者：Chinnappan Sivasankar、Felix Tuczek

  DOI：10.1039/b602038k

  日期：——

  Reaction of [MCl(NEt)(dppe)2]Cl (M = Mo, W) with n-BuLi in tert-butyl methyl ether under an N2 atmosphere yields the M(0) bis(dinitrogen) complexes [M(N2)2(dppe)2] and acetonitrile. A mechanism is proposed for this reaction which involves an anionic chloro–acetonitrile intermediate. The implications of these findings to the chemistry of Mo and W organoimides are discussed.

  在 N2 气氛下，[MCl(NEt)(dppe)2]Cl（M = Mo、W）与叔丁基甲基醚中的 n-BuLi 反应，生成 M(0)双（二氮）络合物 [M(N2)2(dppe)2] 和乙腈。该反应的机理涉及阴离子氯-乙腈中间体。讨论了这些发现对 Mo 和 W 有机酰亚胺化学的影响。
• Dismutation of a Molybdenum(IV) Acetonitrile−NNH₂ Complex to a Molybdenum(IV) Ethylimido Complex + N₂:  Mechanistic Implications on the Protonation of Coordinated Nitriles at the β-Carbon Atom
  作者：Chinnappan Sivasankar、Natascha Böres、Gerhard Peters、Carsten M. Habeck、Felix Studt、Felix Tuczek

  DOI：10.1021/om050220r

  日期：2005.10.1

  Reaction of the Mo(0) depe complex [Mo(N2H2)(depe)2(CH3CN)](OTf)2 (3) (depe = 1,2-bis(diethylphosphino)ethane) with base gives the ethylimido complex [Mo(depe)2(CH3CH2N)(CH3CN)](OTf)2 (10), whereas base treatment of the corresponding dppe complex [Mo(N2H2)(dppe)2(OTf)](OTf) (12; dppe = 1,2-bis(diphenylphosphino)ethane) leads to formation of [Mo(N2)(dppe)2(CH3CN)] (14). Reaction of dinitrogen complex

  Mo（0）配位络合物[Mo（N 2 H 2）（depe）2（CH 3 CN）]（OTf）2（3）（depe = 1,2-双（二乙基膦基）乙烷）与碱反应，得到乙基亚胺基络合物[Mo（depe）2（CH 3 CH 2 N）（CH 3 CN）]（OTf）2（10），而相应的dppe络合物[Mo（N 2 H 2）（dppe）2的碱处理（OTf）]（OTf）（12 ; dppe = 1,2-双（二苯基膦基）乙烷）导致形成[Mo（N 2）（dppe）2（CH 3CN）]（14）。二氮配合物14与HBF 4的反应得到乙基酰亚胺基配合物[Mo（dppe）2（CH 3 CH 2 N）（F）]（BF 4）（17）。配合物3和14中配位乙腈的质子化研究得到相应的乙基亚氨基配合物。提出了以下假设的实验和理论证据，即乙腈仅与诸如三氟甲磺酸盐或氟化物的路易斯碱键合到Mo（0）中心，才被激活向β-碳质子化。膦大肠菌素（depe>
• Reduction of a Coordinated Acetonitrile Ligand:  Synthesis of an Ethylimido Complex of Tungsten
  作者：Leslie D. Field、Neale G. Jones、Peter Turner

  DOI：10.1021/om970829v

  日期：1998.6.1

  Treatment of the dinitrogen complex W(N-2)(2)(dppe)(2) (1; dppe = 1,2-bis(diphenylphosphino)ethane) with trifluoromethanesulfonic acid yields the novel hydrazido complex [W(N2H2)(oTf)(dppe)(2)](+)[oTf](-) (2; OTf = CF3SO3-). The triflato ligand is readily displaced by other ligands and coordinating solvents. The triflato complex 2 yields the complex [W(N2H2)(NCCH3)(dppe)(2)](2+) (5), when it is dissolved in acetonitrile, and 5 is readily deprotonated by a variety of bases to give the acetonitrile-dinitrogen complex W(N-2)(NCCH3)(dppe)(2) (3). Complex 3 is protonated at the beta-carbon by tetrafluoroboric acid, resulting in the reduction of the coordinated nitrile to give the novel imido complex [WF(NCH2CH3)(dppe)(2)](+)[BF4](-)(4). The X-ray crystal structure of the imido complex 4 reveals an effectively linear W-N-C bond (171.8 degrees) in the imido ligand with a W-N bond length of 1.741(4) Angstrom.