TpMe2MoVIO2(SPh) | 129238-83-1

• 英文名称: TpMe2MoVIO2(SPh)
• 英文别名: (hydrotris(3,5-dimethylpyrazol-1-yl)borate)(thiophenolate)dioxomolybdenuv(VI)；{hydrotris(3,5-dimethyl-1-pyrazolyl)borate}dioxomolybdenum(VI)SPh；Tp^Me2Mo^VIO2(SPh)；[(hydridotris(3,5-dimethylpyrazol-1-yl)borate)Mo(VI)O2(SPh)]；(hydridotris(3,5-dimethylpyrazol-1-yl)borate)MoO2(SPh)；Tp*MoO2SPh
• CAS: 129238-83-1
• 化学式: C₂₁H₂₇BMoN₆O₂S
• 分子量: 534.301
• InChiKey: RHUXWEJVPCWBMZ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  3.14
• 重原子数：
  32.0
• 可旋转键数：
  3.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  87.6
• 氢给体数：
  0.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  TpMe2MoVIO2(SPh) 在 (C₆H₅)3P 作用下， 以 二氯甲烷 为溶剂， 生成 {hydrotris(3,5-dimethyl-1-pyrazolyl)borate}oxomolybdenum(V)(Cl)(SPh)
  参考文献：
  名称：

  Roberts, Sue A.; Young, Charles G.; Kipke, Cary A., Inorganic Chemistry, 1990, vol. 29, # 19, p. 3650 - 3656

  摘要：

  DOI：
• 作为产物：
  描述：

  三(3,5-二甲基-1-吡唑基)硼氢化钾 以 二氯甲烷 、 甲苯 为溶剂， 生成 TpMe2MoVIO2(SPh)
  参考文献：
  名称：

  Roberts, Sue A.; Young, Charles G.; Kipke, Cary A., Inorganic Chemistry, 1990, vol. 29, # 19, p. 3650 - 3656

  摘要：

  DOI：

文献信息

• π-Acid/π-Base Carbonyloxomolybdenum(IV) Complexes and Their Oxomolybdenum(VI/IV) Precursors
  作者：Michael S. Malarek、David J. Evans、Paul D. Smith、Ashley R. Bleeker、Jonathan M. White、Charles G. Young

  DOI：10.1021/ic0510314

  日期：2006.3.1

  TpiPrMoO(SR)(NCMe) react with CO gas in toluene. The carbonyloxomolybdenum(IV) complexes exhibit nu(CO) and nu(Mo=O) IR bands at ca. 2025 and 935 cm(-1), respectively, and NMR spectra indicative of C(1) symmetry, with delta(C)(CO) ca. 250. The crystal structure of TpiPrMoO(SiPr)(CO), the first for a mononuclear carbonyloxomolybdenum complex, revealed a distorted octahedral geometry, with d(Mo=O) = 1.683(3)

  当TpiPrMoO（SR）（NCMe）与CO反应时形成棕色TpiPrMoO（SR）（CO）（TpiPr =氢三（3-异丙基吡唑-1-基）硼酸酯; R = Et，iPr，Ph，对甲苯，Bz）甲苯中的气体。羰基氧钼（IV）配合物在大约2时显示nu（CO）和nu（Mo = O）IR带。分别为2025和935 cm（-1），并且NMR光谱指示C（1）对称性，其中delta（C）（CO）约为。250. TpiPrMoO（SiPr）（CO）的晶体结构，是单核羰基氧钼钼配合物的第一个，显示出扭曲的八面体几何形状，d（Mo = O）= 1.683（3）A，d（Mo-C）= 2.043 （5）A，并且角度（O = Mo-C）= 90.87（16）度。蓝绿色乙腈前体是通过使顺式TpiPrMoO2（SR）与PPh3反应生成的；它们是不稳定的，在大约处显示一个nu（Mo = O）红外波段。950 cm（-1），并
• Quantitation of the ligand effect in oxo-transfer reactions of dioxo-Mo(<scp>vi</scp>) trispyrazolyl borate complexes
  作者：Partha Basu、Brian W. Kail、Andrew K. Adams、Victor N. Nemykin

  DOI：10.1039/c2dt32349d

  日期：——

  these reactions proceed via the formation of a phosphoryl intermediate complex that undergoes a solvolysis reaction. We report the synthesis and characterization of several phosphoryl complexes. The rates of formation of phosphoryl complexes and their solvation were determined by spectrophotometry. The rates of the reactions and the properties of the phosphoryl species were investigated using the Quantitative

  硼酸氢化三(3,5-二甲基吡唑基)硼酸酯(氢化三(3,5-二甲基吡唑基)硼酸酯，Tp Me2；氢化三(3-异丙基吡唑-1-基)硼酸酯，Tp i Pr )的二氧-Mo( VI )配合物的氧原子转移反应性(OAT )与叔膦（PME 3，PME 2 PH，PET 3，PET 2 PH，PBU ñ 3，PMePh 2，或PEtPh 2）进行了研究。在乙腈，这些反应通过形成磷酸中间体复合物进行，该复合物经历溶剂分解反应。我们报告了几种磷酰配合物的合成和表征。通过分光光度法测定磷酰配合物的形成速率及其溶剂化。使用配体效应定量分析 (QALE) 方法研究反应速率和磷酰基物质的性质。结果表明，至少在该系统中，反应的第一步主要受空间因子控制，而在第二步中，电子和空间因子都很重要。我们还分析了配体对反应速率的影响，即Tp Me2与Tp i公关。
• Substituent Effect on Oxygen Atom Transfer Reactivity from Oxomolybdenum Centers: Synthesis, Structure, Electrochemistry, and Mechanism
  作者：Partha Basu、Victor N. Nemykin、Raghvendra S. Sengar

  DOI：10.1021/ic900579s

  日期：2009.7.6

  X-ray crystallography. Electronic and NMR spectra, as well as redox potentials vary as a function of substituent on the thiophenolato ligand. When viewed entirety of the oxygen atom transfer (OAT) reactivity, the reaction of Tp*MoO2(S-p-RC6H4) with PMe3 shows a biphasic behavior, indicating the formation of at least one intermediate. The kinetics of the both steps, that is, the formation of the phosphoryl

  通式Tp * MoO 2（S -p -RC 6 H 4）（1）的二氧杂钼配合物，其中Tp * =氢三（3,5-二甲基-1-吡唑基）硼酸酯，R = OMe，Me，SMe， NHCOMe，H，Cl，CF 3，NO 2与三甲基膦（PMe 3）反应，转化为通式Tp * MoO（S- p -RC 6 H 4）（OPMe 3）（2）的配合物（其中R = OMe，Me，SMe，H，Cl和CF 3）。分离出这些络合物，并通过NMR，IR，UV / vis和单晶X射线晶体学进行表征。电子光谱和NMR光谱以及氧化还原电势随硫酚基配体上取代基的变化而变化。当观察到的氧原子转移（OAT）的反应性整体，TP的反应*的MoO 2（S- p -RC 6 ħ 4）用PMe 3示出了两相行为，指示至少一个中间的形成。这两个步骤的动力学，即磷酰基中间体的形成和溶剂配位物种的形成已通过紫外可见光谱法进行了研究。第一步遵循二阶过
• Dioxomolybdenum(VI) Complexes of Tripodal Nitrogen-Donor Ligands: Syntheses and Spectroscopic, Structural, and Electrochemical Studies, Including the Generation of EPR-Active Molybdenum(V) Species in Solution
  作者：Zhiguang Xiao、Michael A. Bruck、Colleen Doyle、John H. Enemark、Carina Grittini、Robert W. Gable、Anthony G. Wedd、Charles G. Young

  DOI：10.1021/ic00128a005

  日期：1995.11

  The dioxo-Mo(VI) complexes LMoO(2)X [L = hydrotris(3,5-dimethylpyrazol-1-yl)borate (L(a)), hydrotris(3-isopropylpyrazol-1-yl)borate (L(b)), hydrotris(3,5-dimethyl-1,2,4-triazol-1-yl)borate (L(c)); X = Cl, Br, NCS, OMe, Oft, OPh, SPri, SPh, SCH(2)Ph] have been synthesized and characterized by spectroscopic and structural methods. The infrared spectra of the complexes exhibit nu(MoO2) bands at 940-920 and 910-890 cm(-1), and the H-1 NMR spectra are indicative of molecular C-s symmetry in solution. The X-ray crystal structures of three complexes are reported. L(a)MoO(2)(SPh): monoclinic space group P2(1)/c, a = 18.265(6) Angstrom, b = 8.110(3) Angstrom, c = 18.299(3) Angstrom, beta = 117.06(2)degrees, V = 2414(1) Angstrom(3) with Z = 4. L(b)MoO2(OMe): monoclinic space group C2/c, a = 30.365(4) Angstrom, beta = 8.373(1) Angstrom, c = 19.646(2) Angstrom, beta = 113.28(1)degrees, V = 4588(1) Angstrom(3) with Z = 8. L(c)MoO(2)(SPh): orthorhombic space group P2(1)2(1)2(1), a = 7.9302(13) Angstrom, b = 16.627(2) Angstrom, c = 17.543(2) Angstrom, V = 2313.1(9) Angstrom(3) with Z = 4. The structures were refined by full-matrix least-squares procedures to R values of 0.043, 0.027, and 0.039, respectively. The mononuclear complexes feature facially tridentate N-donor ligands, mutually cis oxo and X ligands, and distorted octahedral geometries, The alkoxy and thiolate complexes undergo a reversible, one-electron reduction to form the corresponding dioxo-Mo(V) anions [LMo(V)O(2)X](-). The requirements for reversible, one-electron electrochemical reduction of dioxo-Mo(VI) complexes appear to be (i) minimal conformational change, restricting substitution trans to the oxo groups, upon reduction and (ii) a steric or electrostatic barrier to the close approach and dinucleation of the reduced species. A number of oxo-hydroxo-Mo(V) complexes of the type LMo(V)O-(OH)X were generated by protonation of the anions [LMo(V)O2X](-). Chemical reduction by Bu(4)(n)NSH results in the sequential generation of [LMo(V)O(2)X](-) and [LMo(V)O(2)X](-) anions (except for X = OPh, SPh, and SPri, when only [LMo(V)O(2)X](-) is formed). The Mo(V) complexes have been characterized by EPR spectroscopy.
• Xiao, Zhiguang; Young, Charles G.; Enemark, John H., Journal of the American Chemical Society, 1992, vol. 114, p. 9194 - 9195
  作者：Xiao, Zhiguang、Young, Charles G.、Enemark, John H.、Wedd, Anthony G.

  DOI：——

  日期：——