trans,trans-W(CO)2(H)(NO)(PMe3)2 | 136576-09-5

• 英文名称: trans,trans-W(CO)2(H)(NO)(PMe3)2
• 英文别名: trans,trans-{WH(CO)2(NO)(PMe3)2}；[WH(CO)₂(NO)(PMe₃)₂]
• CAS: 136576-09-5
• 化学式: C₈H₁₉NO₃P₂W
• 分子量: 423.041
• InChiKey: MOCPWUXTZGCKFS-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：

  trans,trans-W(CO)2(H)(NO)(PMe3)2 在 CH₃COCH₂COCH₃ 作用下， 以 甲苯 为溶剂， 以75%的产率得到
  参考文献：
  名称：

  Van Der Zeijden, Adolphus A. H.; Veghini, Dario; Berke, Heinz, Inorganic Chemistry, 1992, vol. 31, # 24, p. 5106 - 5116

  摘要：

  DOI：
• 作为产物：
  描述：

  生成 trans,trans-W(CO)2(H)(NO)(PMe3)2 、 trimethylphosphine-borane
  参考文献：
  名称：

  Van Der Zeijden, Adolphus A. H.; Shklover, Valery; Berke, Heinz, Inorganic Chemistry, 1991, vol. 30, # 23, p. 4393 - 4396

  摘要：

  DOI：

文献信息

• Reduction of Aldehydes and Ketones by Transition Metal Hydrides. Part 2. Reaction oftrans,trans-[WH(CO)2(NO)(PMe3)2] with pyridine, functionalized aldehydes, and ketones
  作者：Adolphus A. H. Van Der Zeijden、Heinz Berke

  DOI：10.1002/hlca.19920750211

  日期：1992.3.18

  uted aldehydes and ketones, (pyridin-2-yl)C(O)R where R = H, Me, Ph, pyridin-2-yl, and with 6-methylpyridine-2-carbaldehyde was studied. In all cases, facile insertion of the CO bond into the WH bond was observed, with rapid subsequent extrusionof a coordinated CO ligand affording O,N-bidentate coordinated tungsten alkoxides. Only in case of pyridine-2-carbaldehyde and di(pyridin-2-yl) ketone, the

  的反应反式，反式- [WH（CO）2（NO）（PME 3）2 ]（1）与（吡啶-2-基） -取代的醛和酮，（吡啶-2-基）C（O）研究了其中R = H，Me，Ph，吡啶-2-基和6-甲基吡啶-2-甲醛的R。在所有情况下，观察到CO键容易插入WH键中，随后迅速挤出配位的CO配体，得到O，N-二齿配位的钨醇盐。仅在吡啶-2-甲醛和二（吡啶-2-基）酮的情况下，通过低温NMR可以观察到初始的n 1 O键结合的插入产物是不稳定的中间体。
• Synthesis and Insertion Behavior of Carbonylhydridonitrosyltris(trimethylphosphine)tungsten(0)
  作者：Jürgen Höck、Heiko Jacobsen、Helmut W. Schmalle、Georg R. J. Artus、Thomas Fox、José I. Amor、Frank Bäth、Heinz Berke

  DOI：10.1021/om000838v

  日期：2001.4.1

  For both reactions equilibrium constants have been derived from VT-NMR measurements and ΔH values were calculated (−46 kJ/mol for 7a and −26 kJ/mol for 7b). An accompanying DFT analysis of the W−H bond demonstrated that a higher number of phosphine ligands in a W(CO)4-n(H)(NO)(PMe3)n series increases the hydridic character of the H ligand and induces a stronger bond polarization. The relative ΔH values

  从mer -W（Cl）（CO）（NO）（PMe 3）3（1）开始，描述了两种合成mer -W（CO）（H）（NO）（PMe 3）3（4）的路线。）或硼氢化物复合物聚体-W（η 1 -BH 4）（CO）（NO）（PME 3）3（3）。已经研究了4发生插入反应的倾向。4种发生反应与苯甲醛，丙醛，新戊醛，二苯甲酮，苯乙酮，和丙酮，得到相应的醇盐络合物聚体-W（CO）（NO）（PMe 3）3（OCHR'R''）（R'= H，R''= Ph（5a）; R'= H，R''= CH 2 CH 2 CH 3（5b）； R′＝ H，R′′＝ CH 2 C（CH 3）3（5c）； R′＝ Ph，R′′＝ Ph（5d）； R′＝ CH 3，R′′＝ Ph （5e）； R′＝ CH 3，R′′＝ CH 3（5f））。插入CO 2会生成甲-O络合物mer -W（CO）（NO）（OCHO）（PMe 3）3（6）。4与CO的反应导致PMe
• IR, Multinuclear-NMR, and Structural Studies on [WH(CO)2(NO)(PR3)2]:cis-Influence of Phosphorus Ligands on Hydride Character
  作者：Adolphus A. H. Van Der Zeijden、Christoph Sontag、H. William Bosch、Valery Shklover、Heinz Berke、Daniel Nanz、Wolfgang Von Philipsborn

  DOI：10.1002/hlca.19910740606

  日期：1991.9.18

  A thorough IR and 1H-, 13C-, 31P-, 183W-NMR spectroscopic, and X-ray structural study was carried out on complexes of the type trans, trans-[WH(CO)2(NO)(PR3)2], (R = Et, Me, Ph, i-PrO, MeO, and PhO). Linear correlations could be found between Tolman's parameter X and v(CO), v(WH), v(NO), δ(13C) (CO), as well as 1n(k), k being the H/D exchange rate constant for the hydride in CD3OD. The 1J(183W,31P)

  彻底IR和1 H-，13 C-，31 P-，183 W-NMR光谱和X射线结构研究的类型的复合物进行的反，反- [WH（CO）2（NO）（ PR 3）2 ]，（R ＝ Et，Me，Ph，i-PrO，MeO和PhO）。可以找到托尔曼参数X与v（CO），v（WH），v（NO），δ（13 C）（CO）以及1n（k）之间的线性相关性，k为H / D汇率CD 3 OD中的氢化物常数。的1 Ĵ（183 W，31 P），2 J（31 P，1 H）和2 J（31 P，13 C）以及1 J（183 W，1 H）值与磷配体上R基团的电负性有关。EHT计算适当的W模型复合体的s轨道总体也表明了这一点。[WH（CO）2（NO）（PR 3）2的X射线结构确定[]（R = Me，Ph和MeO）。在WP键长度以及PWP和CWC角度中观察到较小的差异。在X射线数据和光谱参数之间没有发现明显的关系。所有这三个结构都揭示了CO和PR
• Van Der Zeijden, Adolphus A. H.; Bosch, H. William; Berke, Heinz, Organometallics, 1992, vol. 11, # 2, p. 563 - 573
  作者：Van Der Zeijden, Adolphus A. H.、Bosch, H. William、Berke, Heinz

  DOI：——

  日期：——
• Reduction of aldehydes and ketones by transition-metal hydrides. 1. Reaction of trans,trans-WH(CO)2(NO)(PMe3)2 with simple and phenoxy-functionalized aldehydes and ketones
  作者：Adolphus A. H. Van der Zeijden、H. William Bosch、Heinz Berke

  DOI：10.1021/om00042a020

  日期：1992.6

  The reaction of trans,trans-WH(CO)2(NO)(PMe3)2 (1) with propanal and benzaldehyde yields unstable insertion products. The C=O double bond of salicylaldehyde rapidly inserts into the W-H bond of 1, affording the alkoxide 3a. This compound readily isomerizes to the more stable phenolate 3b. In the presence of excess salicylaldehyde 3a and 3b react further to the isolable tungsten salicylates 3c and 3d, respectively, with liberation of the organic reduction product alpha,2-dihydroxytoluene. Compound 3d crystallizes in the monoclinic space group P2(1)/c with a = 8.863 (3) angstrom, b = 10.849 (3) angstrom, c = 19.939 (6) angstrom, beta = 96.31 (2)-degrees, V = 1905.7 (10) angstrom3, Z = 4, and R = 0.0558 for 3402 observed reflections. In the solid-state structure of 3d the salicylate moiety, acting as an O,O'-bidentate ligand to tungsten, shows some quinoid character. Similarly, 1 reacts with 2 equiv of 2-hydroxyacetophenone, producing 4 and 1-(2-hydroxyphenyl)ethanol. Treating 1 with methyl salicylate affords 5, albeit via a simple acid-base reaction with evolution of H-2. Reaction of 1 with 4-hydroxybenzaldehyde initially yields the insertion product 6a, after which an equilibrium reaction between different tungsten phenolates sets in.