pentacarbonyl(1,3-diethylimidazolin-2-ylidene)tungsten(0)

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: pentacarbonyl(1,3-diethylimidazolin-2-ylidene)tungsten(0)
• 英文别名: pentacarbonyl(1,3-diethylimidazolidin-2-ylidene)tungsten；[W(CO)5(1,3-diethyl-4,5-dihydroimidazol-2-ylidene)]；Carbon monoxide;(1,3-diethylimidazolidin-2-ylidene)tungsten
• 化学式: C₁₂H₁₄N₂O₅W
• 分子量: 450.104
• InChiKey: JHTFWMVRXJFPSB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.09
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  11.5
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  pentacarbonyl(1,3-diethylimidazolin-2-ylidene)tungsten(0) 以 二氯甲烷 为溶剂， 生成 [Pd(Cl)2(1,3-diethylimidazolidin-2-ylidene)]2
  参考文献：
  名称：

  N-Heterocyclic Carbene Transfer from Gold(I) to Palladium(II)

  摘要：

  N-Heterocyclic carbene gold(I) complexes [(L)AuCl] [L = 1,3-diethyl-4,5-dihydroimidazol-2-ylidene (3a); 1,3-dibenzyl-4,5-dihydroimidazol-2-ulidene (3c); 1,3-dipicolyl-4,5-dihydroimidazol-2-ylidene (3d); 1,2-diethylimidazol-2-ylidene (5a); and 1-methylthiomethyl-3-mesitylimidazol-2-ylidene (10)] react with [(PhCN)(2)PdCl2] to give the corresponding palladium complexes, and the reactions are promoted by the addition of triphenylphosphine, This Study demonstrates that the carbene moiety can be transferred from Au(I) to Pd(II) for the first time.

  DOI：

  10.1021/om900776j
• 作为产物：
  描述：

  (CO)5W[-CN(CH2)2NH-] 在 sodium hydride 作用下， 以 not given 为溶剂， 生成 pentacarbonyl(1,3-diethylimidazolin-2-ylidene)tungsten(0)
  参考文献：
  名称：

  N-Heterocyclic Carbene Transfer from Gold(I) to Palladium(II)

  摘要：

  N-Heterocyclic carbene gold(I) complexes [(L)AuCl] [L = 1,3-diethyl-4,5-dihydroimidazol-2-ylidene (3a); 1,3-dibenzyl-4,5-dihydroimidazol-2-ulidene (3c); 1,3-dipicolyl-4,5-dihydroimidazol-2-ylidene (3d); 1,2-diethylimidazol-2-ylidene (5a); and 1-methylthiomethyl-3-mesitylimidazol-2-ylidene (10)] react with [(PhCN)(2)PdCl2] to give the corresponding palladium complexes, and the reactions are promoted by the addition of triphenylphosphine, This Study demonstrates that the carbene moiety can be transferred from Au(I) to Pd(II) for the first time.

  DOI：

  10.1021/om900776j

文献信息

• Carbene complexes. Part 10. Electron-rich olefin-based mono-, bis-, and tris-carbene-tungsten(0) complexes and some derived six and seven-co-ordinate mono- and bis-carbene-dihalogenotungsten(II) and related molybdenum(II) species
  作者：Michael F. Lappert、Peter L. Pye

  DOI：10.1039/dt9770001283

  日期：——

  The monocarbene complexes [M(CO)5LR](M = MO or W) behave differently, yielding respectively [ILR][Mo(CO)4I3] or [W(CO)4I2(LR)](R = Me). The frequency ν(CN2) is at 1 500–1 480cm–1for the carbene-tungsten(0), but at 1 530–1 500 cm–1 for the carbene-molybdenum(II) and -tungsten(II), complexes; values of ν(CO) are generally low, in accordance with the strong σ-donor character of the carbene ligand. The value

  稳定的单和双碳烯-钨（0）配合物[W（CO）5 L R ]或顺式-[W（CO）4（L R）2 ] [L R =：[省略图] R（R = Me，Et或CH 2 Ph）]是通过将[W（CO）6 ]与富含电子的烯烃[：[省略图示] R] 2，L R 2加热而获得的。六元螯合烯烃[：[Medium] Me] 2 L' Me 2的反应性较低，仅形成[W（CO）5 L' Me ]。所述顺式-dicarbenetungsten（0）配合物被光化学异构化为反式物种，但很容易热还原为前者。碱与（a）[W（CO）5 L R ]反应生成顺式-[W（CO）4（L R）Q]（Q = PEt 3或PBu n 3），fac- [W（CO）3 L R Q 2 ] [Q = P（OMe）3或P（OPh）3 ]，或连续使用LiR'（R'= Me或Ph）和[OEt 3 ] [BF 4 ]}顺式-[W（ CO）4 C（OEt）R'}
• Metal Ion Mediated Transfer and Cleavage of Diaminocarbene Ligands
  作者：Rong-Zhi Ku、Jen-Chung Huang、Jian-Yang Cho、Fu-Mei Kiang、K. Rajender Reddy、Yi-Chun Chen、Kuo-Jeng Lee、Jung-Hua Lee、Gene-Hsiang Lee、Shie-Ming Peng、Shiuh-Tzung Liu

  DOI：10.1021/om981023d

  日期：1999.5.1

  allyl, benzyl, 4-pentenyl] with (PhCN)2PdCl2, (PhCN)2PtCl2, [(CO)2RhCl]2, (Me2S)AuCl, [(CH3CN)4Cu]BF4, and AgBF4 provide the corresponding diaminocarbene complexes via carbene ligand transfer. The resulting Pd(II), Pt(II), Rh(I), and Au(I) carbene complexes are stable and were isolated. The Cu(I) and Ag(I) complexes readily undergo acid-induced MC cleavage to yield the imidazolidin-2-ylidinium salts. The

  在温和条件下，（CO）5 M C [N（R）CH 2 ] 2 [M = W，Mo，Cr; R ＝ Et，烯丙基，苄基，4-戊烯基]与（PhCN）2 PdCl 2，（PhCN）2 PtCl 2，[（（CO）2 RhCl] 2，（Me 2 S）AuCl，[（CH 3 CN）4 Cu] BF 4和AgBF 4通过卡宾配体转移提供相应的二氨基卡宾配合物。所得的Pd（II），Pt（II），Rh（I）和Au（I）卡宾配合物稳定且已分离。Cu（I）和Ag（I）配合物容易发生酸诱导的MC裂解，得到咪唑烷基-2-基亚胺盐。研究了两个膦供体的卡宾转移反应：（CO）m（L）W C [N（R）CH 2 ] 2 R = Et，苄基; L = PPh 3，m = 4；L = dppe，m = 3}。（CO）5 W C [N（CH 2 C 6 H 5）CH 2 ] 2（1c），顺式-（CO）4（PPh 3）W C [N（CH
• Synthesis of Cyclic Diamino-Substituted Metal Carbene Complexes
  作者：Chung-Yuan Liu、Der-Yi Chen、Gene-Hsiang Lee、Shie-Ming Peng、Shiuh-Tzung Liu

  DOI：10.1021/om950735q

  日期：1996.2.6

  bis(carbene) complex. Deprotonation of the N−H of the carbene complex followed by the reaction of alkyl iodides provided the N-alkylated product. In the case of N-allyl-substituted complexes (CO)5MCNR(CH2)2N(CH2CHCH2) (M = Cr, Mo, W), the carbon−carbon double bond underwent intramolecular ligand displacement of carbonyl ligand to yield the corresponding π-coordinated complex. Unlike the group VI metal carbonyl

  M（CO）6（M = Cr，Mo，W）与RNH（CH 2）n N PPh 3（R = H，Et，Ph; n = 2 ，3、4）形成相应的异氰化物配合物，随后对其进行分子内环化，以高收率得到（CO）5 M CN（R）（CH 2）n NH。卡宾络合物均未与胺-膦亚胺RNH（CH 2）n N PPh 3进一步反应得到双（卡宾）配合物。卡宾配合物的NH的去质子化，然后烷基碘的反应提供了N-烷基化的产物。在N-烯丙基取代的配合物（CO）5 M CNR（CH 2）2 N（CH 2 CH CH 2）（M = Cr，Mo，W）的情况下，碳-碳双键经历了分子内配体的置换羰基配体产生相应的π配位络合物。与第VI族金属羰基配合物不同，用2摩尔当量的Ph 3 P N（CH 2）2 NH 2处理ReBr（CO）5提供了双（卡宾）配合物fac-（CO）3 BrRe（CNHCH 2 CH 2 NH）2。所有配合物均通过
• Coordination chemistry and catalytic activity of N-heterocyclic carbene iridium(i) complexes
  作者：Ching-Feng Fu、Yung-Hung Chang、Yi-Hong Liu、Shei-Ming Peng、Cornelis J. Elsevier、Jwu-Ting Chen、Shiuh-Tzung Liu

  DOI：10.1039/b906016b

  日期：——

  Iridium complexes [(CO)2Ir(NHC-R)Cl] (R = Et-, 3a; PhCH2-, 3b; CH3OCH2CH2-, 3c; o-CH3OC6H4CH2-, 3d; NHC: N-heterocyclic carbene) are prepared via the carbene transfer from [(NHC-R)W(CO)5] to [Ir(COD)Cl]2. By using substitution with 13CO, we are able to estimate the activation energy (G) of the CO-exchange in 3a-d, which are in the range of 12-13 kcal mol-1, significantly higher than those for the phosphine

  通过以下方法制备铱配合物[（CO）2Ir（NHC-R）Cl]（R = Et-，3a; PhCH2-，3b; CH3OCH2CH2-，3c; o-CH3OC6H4CH2-，3d; NHC：N-杂环卡宾）。卡宾从[（NHC-R）W（CO）5]转移到[Ir（COD）Cl] 2。通过使用13CO取代，我们能够估算3a-d中CO交换的活化能（G），其范围为12-13 kcal mol-1，显着高于膦类似物[ （CO）2Ir（PCy3）Cl]。3b和3d与等摩尔量的PPh3反应导致形成相应的[（NHC-R）Ir（CO）（PPh3）Cl]，其中膦和NHC处于反式排列状态。相反，3a或3c与膦的类似反应进行取代，然后进行阴离子复分解，直接生成相应的二取代[[NHC-R] Ir（CO）（PPh3）2] BF4（5）。用过量的PPh3处理3b或3d会产生类似的崩解产物5b和5d。羰基铱配合物的IR数据分析提供
• Biscarbene Palladium(II) Complexes. Reactivity of Saturated Versus Unsaturated <i>N</i>-Heterocyclic Carbenes
  作者：Ching-Feng Fu、Chun-Chin Lee、Yi-Hung Liu、Shie-Ming Peng、Stefan Warsink、Cornelis J. Elsevier、Jwu-Ting Chen、Shiuh-Tzung Liu

  DOI：10.1021/ic9025188

  日期：2010.3.15

  A series of designed palladium biscarbene complexes including saturated and unsaturated N-heterocyclic carbene (NHC) moieties have been prepared by the carbene transfer methods. All of these complexes have been characterized by H-1 and C-13 NMR spectroscopy as well as X-ray diffraction analysis, The reactivity of Pd-C-(saturated NHC) is distinct from that of Pd-C-(unsaturated NHC). The Pd-C-(saturated NHC) bonds are fairly stable toward reagents such as CF3COOH, AgBF4 and I-2, whereas Pd-C-(unsaturated NHC) bonds are readily cleaved under the similar conditions. Notably, the catalytically activity of these palladium complexes on Suzuki-Miyaura coupling follows the order: (sat-NHC)(2)PdCl2 > (sat-NHC)(unsat-NHC)PdCl2 > (unsat-NHC)(2)PdCl2.