(CO)2Ni(P(C2H5)3)2 | 16787-33-0

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: (CO)2Ni(P(C2H5)3)2
• 英文别名: carbon monoxide;nickel;triethylphosphane
• CAS: 16787-33-0
• 化学式: C₁₄H₃₀NiO₂P₂
• 分子量: 351.029
• InChiKey: DQJXTQOCZLXDDI-UHFFFAOYSA-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：

  (CO)2Ni(P(C2H5)3)2 在 盐酸 作用下， 以 乙醇 、 水 为溶剂， 生成 bis(triethylphosphine)nickel(II) chloride 、 二氧化碳 、 一氧化碳 、 氢气
  参考文献：
  名称：

  NiX 2-叔膦体系对水煤气变换反应的均相催化

  摘要：

  所述NIX 2大号2（X =氯，溴; L = PME 3 PET 3 PBut 3，P（I-PR）3，PME 2 PH，PET 2 PH）水-醇溶液，催化水煤气变换反应（WGSR ），一氧化碳，大气压和高于90°C的温度。该催化作用通过以下主要反应完成：NiX 2 L 2 + 3CO + H 2 O→Ni（CO）2 L 2 + 2HX + CO 2；Ni（CO）2 L 2 + 2HX + CO 2；Ni（CO）2 L 2 + 2HX + CO 2。Ni（CO）2 L 2 + 2HX→NiX 2 L 2 + H2，也可以单独进行。催化活性随时间缓慢降低，顺序为：PR 3

  DOI：

  10.1016/s0020-1693(00)87578-7
• 作为产物：
  描述：

  (cis-C6H5CHCH)Ni(P(C2H5)3)2Br 在 CO 作用下， 以 甲醇 为溶剂， 以97.5%的产率得到(CO)2Ni(P(C2H5)3)2
  参考文献：
  名称：

  Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Ni: Org.Verb.1, 1.1.1.1.1, page 10 - 26

  摘要：

  DOI：

文献信息

• Insertion of Carbon Monoxide into Nickel-Alkyl Bonds of Monoalkyl-and Dialkylnickel(II) Complexes, NiR(Y)L₂and NiR₂L₂. Preparation of Ni(COR)(Y)L₂from NiR(Y)L₂and Selective Formation of Ketone, Diketone, and Aldehyde from NiR₂L₂
  作者：Takakazu Yamamoto、Teiji Kohara、Akio Yamamoto

  DOI：10.1246/bcsj.54.2161

  日期：1981.7

  Reactions of monoalkylnickel(II) complexes, NiR(Y)L2 (R=CH3, C2H5; Y=Cl, suc(succinimido), pht(phthalimido), OC6H4-p-CN; L=1/2 bpy (2,2′-bipyridine), PEt3 (triethylphosphine)), with CO afford monoacylnickel(II) complexes, Ni(COR)(Y)L2, which are characterized by elemental analysis and spectroscopies (IR and NMR). Reactions of the acylnickel(II) complexes with alcohols and aniline give the corresponding esters and amides, respectively. Exposure of Ni(COR)(Y)L2 to dry air leads to oxidation of RCO to a RCOO ligand giving a complex formulated as Ni(OCOR)(Y)L2. Reactions of dimethylnickel(II) complexes, Ni(CH3)2L2 (L=1/2 bpy, PEt3, 1/2 dpe (1,2-bis(diphenylphosphino)ethane, 1/2 dpp (1,3-bis(diphenylphosphino)propane), with carbon monoxide afford acetone and/or 2,3-butanedione in medium to high yields, the acetone/2,3-butanedione ratio varying with the ligand L, reaction temperature, and additives such as maleic anhydride and triphenylphosphine. Generally the acetone/2,3-butanedione ratio decreases with increase in thermal stabilities of Ni(CH3)2L2. Ni(C2H5)2(bpy) and Ni(n-C3H7)2(bpy) give 3-pentanone and 4-heptanone, respectively, on treating them with CO, whereas Ni(C2H5)2(dpe) produces C2H5CHO and C2H4.

  甲基或乙基镍(II)配合物NiR(Y)L2 (R=CH3, C2H5; Y=Cl, succ(琥珀酰亚胺), pht(酞酰亚胺), OC6H4-p-CN; L=1/2 bpy (2,2'-联吡啶), PEt3 (三乙基膦))与CO反应生成单酰基镍(II)配合物Ni(COR)(Y)L2, 该化合物通过元素分析和光谱学(IR和NMR)进行表征。酰基镍(II)配合物与醇和苯胺反应生成相应的酯和酰胺。将Ni(COR)(Y)L2暴露于干燥空气中会导致RCO氧化成RCOO配体, 生成化学式为Ni(OCOR)(Y)L2的配合物。二甲基镍(II)配合物Ni( )2L2 (L=1/2 bpy, PEt3, 1/2 dpe (1,2-双(二苯基膦)乙烷), 1/2 dpp (1,3-双(二苯基膦)丙烷))与一氧化碳反应生成中等至高产率丙酮和/或2,3-丁二酮, 丙酮/2,3-丁二酮的比例随配体L、反应温度和马来酸酐及三苯基膦等添加剂的不同而变化。通常, 随着Ni( )2L2热稳定性的增加, 丙酮/2,3-丁二酮的比例下降。Ni( )2(bpy)和Ni(n-C3H7)2(bpy)用CO处理分别生成3-戊酮和4-庚酮, 而Ni( )2(dpe)生成 CHO和C2H4.
• Oxidative Addition of Esters of Formic Acid and β-Lactones to Ni(0)-Complexes Involving Cleavage of the C–O Bond
  作者：Takakazu Yamamoto、Junichi Ishizu、Akio Yamamoto

  DOI：10.1246/bcsj.55.623

  日期：1982.2

  CH2C6H5), with Ni(0)-complexes (mixtures of bis(1,5-cyclooctadiene)nickel (Ni(cod)2) and tertiary phosphines (PR′3)) lead to decarbonylation of HCOOR to afford (Ni(CO)n (PR″3)4−n and ROH. Vinyl formate gives a mixture of CH3CHO, Ni(CO)n(PR′3)4−n, C2H4, and CO2 on interaction with the Ni(0)-complexes. β-Lactones liberate CO2 on treatment with the Ni(0)-complexes. Oxidative addition of the reactants to

  甲酸酯 HCOOR (R=C2H5, CH2C6H5) 与 Ni(0)-配合物（双（1,5-环辛二烯）镍 (Ni(cod)2) 和叔膦 (PR'3) 的混合物）的反应) 导致 HCOOR 脱羰得到 (Ni(CO)n (PR"3)4-n 和 ROH。甲酸乙烯酯得到 CH3CHO、Ni(CO)n(PR'3)4-n、C2H4 和CO2 与 Ni(0)-络合物相互作用。β-内酯在用 Ni(0)-络合物处理时释放 。反应物氧化加成到 Ni，包括 C-O 键的断裂导致形成的产品。
• Successive insertion of tetrafluoroethylene and CO and of tetrafluoroethylene and acetylenes into aryne–nickel(0) bonds
  作者：Martin A. Bennett、Margaret Glewis、David C. R. Hockless、Eric Wenger

  DOI：10.1039/a702375h

  日期：——

  Aryne–nickel complexes [Ni(η 2 -C 6 H 4 )L 2 ] [L 2 = 2PEt 3 or dcpe; dcpe = (C 6 H 11 ) 2 PCH 2 CH 2 P(C 6 H 11 ) 2 ] and [Ni(η 2 -C 10 H 6 )(PEt 3 ) 2 ] reacted readily with C 2 F 4 to form the corresponding five-membered tetrafluoro-substituted nickelacycles [Ni(C 6 H 4 CF 2 CF 2 -2)L 2 ] (L 2 = dcpe or 2PEt 3 ) and [Ni(2-C 10 H 6 CF 2 CF 2 -3)(PEt 3 ) 2 ], respectively. The complex [Ni(C 6 H 4 CF 2 CF 2 -2)(dcpe)] is very stable towards air, whereas the PEt 3 analogues react readily to give µ-aryloxo dimers. The naphthalene-based dimer [Ni(µ-2-OC 10 H 6 CF 2 CF 2 -3)(PEt 3 )} 2 ] has been structurally characterized. The complexes [Ni(C 6 H 4 CF 2 CF 2 -2)L 2 ] insert CO into their aryl–nickel bonds to form six-membered acyl complexes [NiC(O)C 6 H 4 CF 2 C F 2 -2}L 2 ] (L 2 = dcpe or 2PEt 3 ) and, after CO-induced reductive elimination, 2,2,3,3-tetrafluoroindanone. The dcpe acyl complex has also been shown to undergo reaction with air to form the carboxylato complex [NiOC(O)C 6 H 4 CF 2 C F 2 -2}(dcpe)], whose structure has been confirmed by X-ray crystallography. Some insertions of acetylenes into the aryl–nickel bonds of [Ni(C 6 H 4 CF 2 CF 2 -2)L 2 ] are also reported.

  Aryne–镍配合物 [Ni(η²-C6H4)L2] [L2 = 2PEt3或dcpe；dcpe = (C6H11)2PCH2CH2P( )2] 和 [Ni(η²-C10H6)(PEt3)2] 很容易与C2F4反应，形成相应的五元四氟取代镍环 [Ni( CF2CF2-2)L2] (L2 = dcpe或2PEt3) 和 [Ni(2- CF2CF2-3)(PEt3)2]。配合物 [Ni( CF2CF2-2)(dcpe)] 对空气非常稳定，而PEt3 的类似物则容易反应生成μ-芳氧二聚体。基于萘的二聚体 [Ni(μ-2-O CF2CF2-3)(PEt3)}2] 已被结构表征。配合物 [Ni( CF2CF2-2)L2] 将CO插入其芳基–镍键，形成六元酰基配合物 [NiC(O) CF2CF2-2}L2] (L2 = dcpe或2PEt3)，并在CO诱导下进行还原消除，生成2,2,3,3-四氟印酮。dcpe 酰基配合物也已被证明可以与空气反应形成羧酸盐配合物 [NiOC(O) CF2CF2-2}(dcpe)]，其结构已通过X射线晶体学确认。也有一些关于碳乙炔插入 [Ni( CF2CF2-2)L2] 中芳基–镍键的报道。
• PREPARATION OF ACYL(CARBOXYLATO)NICKEL AND -PALLADIUM COMPLEXES M(COR)(OCOR’)L₂(M = Ni, Pd) AND REVERSIBLE REDUCTIVE ELIMINATION OF CARBOXYLIC ANHYDRIDES, RCOOCOR’
  作者：Sanshiro Komiya、Akio Yamamoto、Takakazu Yamamoto

  DOI：10.1246/cl.1981.193

  日期：1981.2.5

  Acyl(carboxylato)nickel(II) and -palladium(II) complexes, M(COR)(OCOR’)L2 2 are prepared by 1 : 1 reactions of MR(OCOR’)L2 1 with CO at −78°, whereas similar reactions in the presence of excess CO at room temperature afford the reductive elimination products, RCOOCOR’. Acid anhydrides add oxidatively to an Ni(0)-complex to afford a complex of the type 2.

  酰基(羧基)镍(II)和-钯(II)配合物M(COR)(OCOR')L2 2 通过MR(OCOR')L2 1 与CO在-78°的1:1反应制备，而类似的在室温下在过量 CO 存在下的反应提供还原消除产物 RCOOCOR'。酸酐与 Ni(0)-配合物氧化加成，得到 2 型配合物。
• Carbonylation of cyano(phenyl)bisligand-nickel(II) complexes and related reactions of benzoyl cyanide with nickel(0) complexes
  作者：G. Favero

  DOI：10.1016/s0022-328x(00)90519-9

  日期：1980.12

  Carbonylation of the complexes Ni(CN)(C6H5)(P)2 (P = P(C2H5)3; P(cyclo-C6H11)3; 12(C2H5)2P(CH2)4P(C2H5)2) affords the acyl-derivatives Ni(CN)(COC6H5)(P)n (n = 1, 2) which, in the presence of excess CO, undergo reductive elimination of C6H5COCN. It has been shown that C6H5COCN reacts with the NiPn (n = 2, 4) complexes to give molecular adducts in which the organic reagent is coordinated to the nickel atom through

  配合物的羰基化Ni（CN）（C 6 H 5）（P）2（P = P（C 2 H 5）3 ; P（环-C 6 H 11）3 ; 12（C 2 H 5）2 P （CH 2）4 P（C 2 H ^ 5）2），得到酰基衍生物的Ni（CN）（COC 6 H ^ 5）（P）ñ（ñ = 1，2），在过量的CO的存在下，经过还原消除C 6 H 5COCN。已经表明，C 6 H 5 COCN与NiP n（n = 2，4）配合物反应生成分子加合物，其中有机试剂通过CO双键与镍原子配位。这些加合物在环境条件下不稳定，并分解为Ni（CN）（C 6 H 5）（P）2和羰基（膦基）镍（0）配合物。