W(CO)3(P(isopropyl)3)2 | 88211-57-8

• 英文名称: W(CO)3(P(isopropyl)3)2
• 英文别名: [W(triisopropylphosphine)2(CO)3]；W(P(i)Pr3)2(CO)3
• CAS: 88211-57-8
• 化学式: C₂₁H₄₂O₃P₂W
• 分子量: 588.36
• InChiKey: WURXVOVHUJWANM-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：

  W(CO)3(P(isopropyl)3)2 在 HI 作用下， 以 甲苯 为溶剂， 生成
  参考文献：
  名称：

  Lang, Russell F.; Ju, Telvin D.; Kiss, Gabor, Journal of the American Chemical Society, 1994, vol. 116, p. 7917 - 7918

  摘要：

  DOI：
• 作为产物：
  描述：

  (η2-dihydrogen)W(CO)3(triisopropylphoshine)2 以 甲苯 为溶剂， 生成 W(CO)3(P(isopropyl)3)2
  参考文献：
  名称：

  可分离分子氢复合物的第一个例子的表征，M(CO)3(PR3)2(H2)（M = 钼或钨；R = Cy 或异丙基）。侧面键合二氢配体的证据

  摘要：

  制备标准反应 de H 2 avec M(CO) 3 (PR 3 ) 2 。练习曲 RX et IR et Raman des Structures

  DOI：

  10.1021/ja00314a049

文献信息

• Molecular hydrogen complexes of the transition metals. 2. Preparation, structure, and reactivity of W(CO)3(PCy3)2 and W(CO)3(P-iso-Pr3)2, .eta.2-H2 complex precursors exhibiting metal.cntdot..cntdot..cntdot.hydrogen-carbon interaction
  作者：Harvey J. Wasserman、Gregory J. Kubas、Robert R. Ryan

  DOI：10.1021/ja00269a027

  日期：1986.4

  electronically unsaturated complexes M(CO)/sub 3/(PR/sub 3/)/sub 2/ (M = Mo, W; R = Cy, i-Pr) are described. Ligands that bind reversibly to W(CO)/sub 3/(PCy/sub 3/)/sub 2/ include H/sub 2/, N/sub 2/, C/sub 2/H/sub 4/, H/sub 2/O, ROH, and thiophene; irreversibly bound ligands are MeCN, pyridine, NH/sub 3/, CyNH/sub 2/, and PR/sub 3/. The structures of W(CO)/sub 3/(PCy/sub 3/)/sub 2/ and W(CO)/sub 3/(P(i-Pr)/sub

  描述了配位和电子不饱和配合物 M(CO)/sub 3/(PR/sub 3/)/sub 2/ (M = Mo, W; R = Cy, i-Pr) 的合成、反应性和分子结构. 与 W(CO)/sub 3/(PCy/sub 3/)/sub 2/ 可逆结合的配体包括 H/sub 2/、N/sub 2/、C/sub 2/H/sub 4/、H/ sub 2/O、ROH和噻吩；不可逆结合的配体是 MeCN、吡啶、NH/sub 3/、CyNH/sub 2/ 和 PR/sub 3/。W(CO)/sub 3/(PCy/sub 3/)/sub 2/ 和 W(CO)/sub 3/(P(i-Pr)/sub 3/)/sub 2/ 的结构涉及初期分子内将远端膦 CH 键氧化加成到金属上。W(CO)/sub 3/(PCy/sub 3/)/sub 2/ 中的三中心 M...HC 相互作用具有 WH(11a)-C(11) =
• Comparison of Thermodynamic and Kinetic Aspects of Oxidative Addition of PhE−EPh (E = S, Se, Te) to Mo(CO)₃(PR₃)₂, W(CO)₃(PR₃)₂, and Mo(N[^tBu]Ar)₃ Complexes. The Role of Oxidation State and Ancillary Ligands in Metal Complex Induced Chalcogenyl Radical Generation
  作者：James E. McDonough、John J. Weir、Kengkaj Sukcharoenphon、Carl D. Hoff、Olga P. Kryatova、Elena V. Rybak-Akimova、Brian L. Scott、Gregory J. Kubas、Arjun Mendiratta、Christopher C. Cummins

  DOI：10.1021/ja063250+

  日期：2006.8.1

  PhE-EPh (E = S, Se, Te) to the M(0) complexes M(PiPr3)2(CO)3 (M = Mo, W) to form stable complexes M(*EPh)(PiPr3)2(CO)3 are reported and compared to analogous data for addition to the Mo(III) complexes Mo(N[tBu]Ar)3 (Ar = 3,5-C6H3Me2) to form diamagnetic Mo(IV) phenyl chalcogenide complexes Mo(N[tBu]Ar)3(EPh). Reactions are increasingly exothermic based on metal complex, Mo(PiPr3)2(CO)3 < W(PiPr3)2(CO)3 <

  PhE-EPh (E = S, Se, Te) 氧化加成到 M(0) 复合物 M(PiPr3)2(CO)3 (M = Mo, W) 形成稳定复合物 M(*EPh)(报告了 PiPr3)2(CO)3 并与添加到 Mo(III) 配合物 Mo(N[tBu]Ar)3 (Ar = 3,5-C6H3Me2) 以形成抗磁性 Mo(IV) 苯基硫属元素化物的类似数据进行比较络合物 Mo(N[tBu]Ar)3(EPh)。基于金属络合物，反应越来越放热，Mo(PiPr3)2(CO)3 < W(PiPr3)2(CO)3 < Mo(N[tBu]Ar)3，就硫属化物而言，PhTe-TePh < PhSe -SePh < PhS-SPh。这些数据用于计算 LnM-EPh 键强度，用于估计当二硫属化物与特定金属络合物相互作用时产生游离 *EPh 自由基的能量。为了测试这些数据，通过停流动力学研究了 Mo(N[tBu]Ar)3
• Kinetic and Thermodynamic Studies of the Reactivity of (Trimethylsilyl)diazomethane with HMo(CO)₃(C₅R₅) (R = H, Me). Estimation of the Mo−N₂CH₂SiMe₃ Bond Strength and Experimental Determination of the Enthalpy of Formation of (Trimethylsilyl)diazomethane
  作者：George C. Fortman、Derek Isrow、James E. McDonough、Paul von Ragué Schleyer、Henry F. Schaefer、Brian Scott、Gregory J. Kubas、Tamás Kégl、Ferenc Ungváry、Carl D. Hoff

  DOI：10.1021/om800336p

  日期：2008.10.13

  )3 with 2 equiv of HMo(CO)3Cp produces SiMe4, Mo(N2)(PiPr3)2(CO)3, and [Mo(CO)3Cp]2. In the presence of excess N2CHSiMe3 this reaction is catalytic and has been used to experimentally measure the heat of hydrogenation of N2CHSiMe3 to N2 and SiMe4 by 2 equiv of HMo(CO)3Cp. The derived enthalpy of formation of N2CHSiMe3 (5.8 ± 3.0 kcal/mol) is in reasonable agreement with high-level theoretical calculations

  N中的反应速率2 CHSiMe 3与HMO（CO）3的CP（CP =η 5 -C 5 H ^ 5）的庚烷服从速率定律-d [HMO（CO）3的CP] / d吨= ķ [HMO （CO）3的CP] [N 2 CHSiMe 3 ]（ķ = 0.035±0.01M的-1小号-1在0℃;Δ ħ ⧧ = 11.7±2.0千卡/摩尔和Δ小号⧧ = -22.0±3.0卡/ （MOl K））。D MO（CO）3 CP和N 2 C H之间的同位素加扰SiMe 3的发生速度快于整个反应的速度。可逆的1,2-加成，形成紧密结合的中间体[我3 SICH 2 Ñ β = N α δ+ ] [ δ-沫（CO）3的CP]提出作为反应的第一步。光谱和计算数据支持这一表述。接触离子对可以经历离子的异源裂解或自由基的均质裂解，并且溶剂对k obs的影响（THF>甲苯>庚烷）可以用该模型来解释。该反应的焓已通过溶液量热法在272
• Wolfram(0)-komplexe des π-aciden N-methylpyrazinium-kations und des N-methylpyrazinium-radikals. Kristall- und molekülstruktur von [(C4H4N2-Me)W(CO)3(PCy3)2] (PF6), Cy  cyclohexyl
  作者：Wolfgang Bruns、Hans-Dieter Hausen、Wolfgang Kaim、Andreas Schulz

  DOI：10.1016/0022-328x(93)83064-3

  日期：1993.2

  16 valence electron species W(CO)3(PR3)2 (R iPr or Cy (cyclohexyl)) were determined by studying stable complexes with the poorly 2e-donating but strongly π-accepting cationic ligand N- methylpyrazinium (mpz+). In comparison with the related complex with W(CO)5, the 1H NMR and electrochemical data suggest a very strong degree of π back-donation from W(CO)3(PR3)2 to the cationic acceptor in the ground

  的粘合特性的二氢配位16个价电子物种W（CO）3（PR 3）2（R我镨或成分Cy（环己基））中通过研究稳定的复合物与不良2E供但强烈π接受性阳离子确定配体N-甲基吡嗪鎓（mpz +）。与具有W（CO）5的相关配合物相比，1 H NMR和电化学数据表明，从W（CO）3（PR 3）2到基态的阳离子受体的π背电荷非常强。[（mpz）W（CO）3的晶体结构分析支持该视图（PCy 3）2 ]（PF 6）揭示了具有异常短的WN键（210.1（10）pm）的反式构型。还原成N-甲基吡嗪鎓自由基络合物可产生高度分辨的ESR光谱，在三羰基络合物的情况下，该光谱显示一种膦配体的损失。但是，即使W（CO）3（PR 3）片段也会引起自吡嗪鎓自由基配体到金属的大量自旋离域。
• Experimental and Computational Studies of Binding of Dinitrogen, Nitriles, Azides, Diazoalkanes, Pyridine, and Pyrazines to M(PR₃)₂(CO)₃ (M = Mo, W; R = Me, ⁱPr).
  作者：Patrick Achord、Etsuko Fujita、James T. Muckerman、Brian Scott、George C. Fortman、Manuel Temprado、Xiaochen Cai、Burjor Captain、Derek Isrow、John J. Weir、James Eric McDonough、Carl D. Hoff

  DOI：10.1021/ic900764e

  日期：2009.8.17

  The enthalpies of binding of a number of N-donor ligands to the complex Mo((PPr3)-Pr-i)(2)(CO)(3) in toluene have been determined by solution calorimetry and equilibrium measurements. The measured binding enthalpies span a range of similar to 10 kcal mol(-1): Delta H-binding=-8.8 +/- 11.2 (N-2-Mo((PPr3)-Pr-i)(2)(CO)(3)); -10.3 +/- 0.8 (N-2); -11.2 +/- 0.4 (AdN(3) (Ad=1-adamantyl)); -13.8 +/- 0.5(N2CHSiMe3); -14.9 +/- 0.9 (pyrazine=pz); -14.8 +/- 0.6 (2,6-Me(2)PZ); -15.5 +/- 1.8 (Me2NCN); -16.6 +/- 0.4 (CH3CN); -17.0 +/- 0.4 (pyridine); -17.5 +/- 0.8 ([4-CH(3)pz][PF6] (in tetrahydrofuran)); -17.6 +/- 0.4 (C6H5CN); -18.6 +/- 1.8 (N2CHC (=O)OEt); and -19.3 +/- 2.5 kcal mol(-1) (pz)Mo((PPr3)-Pr-i)(2)(CO)(3)). The value for the isonitrile AdNC (-29.0 +/- 0.3) is 12.3 kcal mol(-1) more exothermic than that of the nitrile AdCN (-16.7 +/- 0.6 kcal mol(-1)). The enthalpies of binding of a range of arene nitrile ligands were also studied, and remarkably, most nitrile complexes were clustered within a 1 kcal mol(-1) range despite dramatic color changes and variation of v(CN). Computed structural and spectroscopic parameters for the complexes Mo ((PPr3)-Pr-i)(2)(CO)(3)L are in good agreement with experimental data. Computed binding enthalpies for Mo((PPr3)-Pr-i)(2)(CO)(3)L exhibit considerable scatter and are generally smaller compared to the experimental values, but relative agreement is reasonable. Computed enthalpies of binding using a larger basis set for Mo(PMe3)(2)(CO)(3)L show a better fit to experimental data than that for Mo((PPr3)-Pr-i)(2)(CO)(3)L using a smaller basis set. Crystal structures of Mo((PPr3)-Pr-i)(2)(CO)(3)(AdCN), W((PPr3)-Pr-i)(2)(CO)(3)(Me2NCN), W ((PPr3)-Pr-i)(2)(CO)(3)(2,6-F2C6H3CN), W((PPr3)-Pr-i)(2)(CO)(3)(2,4,6-Me3C6H2CN), W((PPr3)-Pr-i)(2)(CO)(3)(2,6-Me(2)pz), W((PPr3)-Pr-i)(2)(CO)(3)(AdCN), Mo((PPr3)-Pr-i)(2)(CO)(3)(AdNC), and W((PPr3)-Pr-i)(2)(CO)(3)(AdNC) are reported.