(Triphos)MoCl₃ | 178457-45-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (Triphos)MoCl₃
• 英文别名: MoCl3(triphos)；[MoCl3(bis(2-diphenylphosphinoethyl)phenylphosphine)]；[MoCl3(dpepp)]；[MoCl3(PhP(CH2CH2PPh2)2)]；bis(2-diphenylphosphanylethyl)-phenylphosphane;trichloromolybdenum
• CAS: 178457-45-9
• 化学式: C₃₄H₃₃Cl₃MoP₃
• 分子量: 736.856
• InChiKey: KBNDQSJITQCWDN-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  9.13
• 重原子数：
  41.0
• 可旋转键数：
  5.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  (Triphos)MoCl₃ 在 Zn/Hg 、 triphenylphosphine 、 N₂ 作用下， 以 四氢呋喃 为溶剂， 以28%的产率得到Mo(N2)2(triphos)(PPh3)
  参考文献：
  名称：

  Electrochemical generation of low-valent molybdenum tri-tertiary phosphine complexes: interactions with monophosphines and molecular nitrogen

  摘要：

  The electrochemical reduction of the 15-electron molybdenum(III) complex [MoCl3(dpepp)], dpepp = Ph2PCH2CH2P(Ph)CH2CH2PPh2, has been studied in the presence of PPh3 under argon and under molecular nitrogen. The primary reduction of the trichloride involves a reversible single-electron transfer to give the unstable 1 6-electron molybdenum(II) anion [MoCl3(dpepp)]-. Loss of chloride from this anion prior to or following further electron transfer provides two principal pathways to molybdenum(o) products, [Mo(eta-6-C6H5PPh2)(dpepp)] under Ar or cis-[Mo(N2)2(dpepp)(PPh3)] under molecular nitrogen, a relatively high potential pathway via molybdenum(i) solvated intermediates and a low potential pathway via trans- [MoCl2(dpepp) (PPh3)]. The cis-dinitrogen complex is unstable on the preparative time-scale, small amounts of trans- [Mo(N2)2(dpepp) (PPh3] are formed, presumably by isomerisation, but the major product is the eta-6-arene complex.

  DOI：

  10.1039/dt9920002263
• 作为产物：
  描述：

  trichlorotris(tetrahydrofuran)molybdenum(III) 、 双(2-二苯基膦乙基)苯基磷 以 四氢呋喃 为溶剂， 生成 (Triphos)MoCl₃
  参考文献：
  名称：

  Ancillary Ligand Effects on Carbon Dioxide-Ethylene Coupling at Zerovalent Molybdenum

  摘要：

  A series of zerovalent molybdenum complexes bearing triphosphine ligands, [Ar2PCH2CH2](2)PPh, have been synthesized and evaluated for reductive functionalization of CO2 with ethylene. The ability to form dimeric triphosphine molybdenum(U) acrylate hydride species from CO2-ethylene coupling was found to be highly sensitive to steric encumbrance on the phosphine aryl substituents. Trapping of triphosphine molybdenum(II) acrylate hydride species using triphenylphosphine afforded isolable monomeric CO2 functionalization products with all ancillary ligands studied. Kinetic analysis of the acrylate formation reaction revealed a first-order dependence on molybdenum, but no influence from CO2 pressure or the triphenylphosphine trap. Systematic attenuation of steric and electronic features of the triphosphine ligands showed a strong CO2 functionalization rate influence for ligand size with [(3,5-Bu-t-C6H3)(2)PCH2CH2](2)PPh coupling nearly four times slower than with [(3,5-Me-C6H3)(2)PCH2CH2](2)PPh. A considerably milder electronic effect was observed with complexes bearing [(4-F-C6H4)(2)PCH2CH2](2)PPh reducing CO2 at approximately half the rate as with [Ph2PCH2CH2](2)PPh.

  DOI：

  10.1021/om500324h

文献信息

• Reactions of coordinated dinitrogen. 16. New mono-dinitrogen complexes of molybdenum that produce ammonia and hydrazine
  作者：T. Adrian George、Robert C. Tisdale

  DOI：10.1021/ja00304a020

  日期：1985.9

  Preparation des complexes Mo(N 2 )(triphos)L 2 (L 2 =2 PPhMe 2 ; Me 2 PCH 2 PMe 2 , 1,2-(Me 2 As) 2 C 6 H 4 , Ph 2 PCH 2 PPh 2 , Ph 2 PCH 2 CH 2 PPh 2 ). Les reactions avec HBr dans CH 2 Cl 2 donnent NH 3 , hydrazine et N 2

  制备复合物 Mo(N 2 )(triphos)L 2 (L 2 =2 PPhMe 2 ; Me 2 PCH 2 PMe 2 , 1,2-(Me 2 As) 2 C 6 H 4 , Ph 2 PCH 2 PPh 2 , Ph 2 PCH 2 CH 2 PPh 2 )。Les 反应 avec HBr dans CH 2 Cl 2 donnent NH 3 , hydrazine et N 2
• Kinetics and Mechanism of Molybdenum-Mediated Acrylate Formation from Carbon Dioxide and Ethylene
  作者：Wesley H. Bernskoetter、Brian T. Tyler

  DOI：10.1021/om100891m

  日期：2011.2.14

  addition to the observation of a formally molybdenum(0) carbon dioxide−ethylene intermediate along the reaction pathway. Acrylate formation from the molybdenum(0) intermediate proceeds with a rate constant of 3.8(3) × 10−5 s−1 and an isotope effect of 1.2(2) for C2H4 vs C2D4 at 23 °C. Measuring rate constants of the CO2 reduction over a 40 °C temperature range established activation parameters for acrylate

  发现零价钼络合物[（Ph 2 PCH 2 CH 2）2 PPh] Mo（C 2 H 4）（N 2）2可以促进CO 2的偶联。和乙烯，得到丙烯酸钼（II）氢化物配合物。通过光谱学和反应性研究确定了丙烯酸钼（II）氢化物配合物的身份。除沿反应路径观察到正式的钼（0）二氧化碳-乙烯中间体外，还通过一系列动力学和同位素标记研究研究了用乙烯进行二氧化碳功能化的机理。由钼（0）中间体形成丙烯酸酯的速率常数为3.8（3）×10 -5 s -1，在23°C下C 2 H 4与C 2 D 4的同位素效应为1.2（2）。测量CO 2的速率常数在40°C的温度范围内还原，建立了丙烯酸酯形成的活化参数ΔS ‡ = 1（7）eu和ΔH ‡ = 24（3）kcal / mol。提出CO 2-乙烯偶联的机理是从钼（0）二氧化碳-乙烯加合物通过限速氧化CC键形成，然后从金属内酯配合物中快速消除β-氢化物而进行的。
• Spectroscopic Characterization of Molybdenum Dinitrogen Complexes Containing a Combination of Di- and Triphosphine Coligands: ³¹P NMR Analysis of Five-Spin Systems
  作者：Kristina Klatt、Gerald Stephan、Gerhard Peters、Felix Tuczek

  DOI：10.1021/ic800389g

  日期：2008.7.1

  The three molybdenum-N2 complexes [Mo(N2)(dpepp)(depe)] (1), [Mo(N2)(dpepp)(dppe)] (2), and [Mo(N2)(dpepp)(1,2-dppp)] (3), all of which contain a combination of a bi- and a tridentate phosphine ligand, were prepared and investigated by vibrational and (31)P NMR spectroscopy. As a tridentate ligand bis(2-diphenylphosphinoethyl)phenylphosphine (dpepp) has been employed. The three different bidentate

  三种钼-N2络合物[Mo（N2）（dpepp）（depe）]（1），[Mo（N2）（dpepp）（dppe）]（2）和[Mo（N2）（dpepp）（1， 2-dppp）]（3）均包含双齿和三齿膦配体的组合，并通过振动和（31）P NMR光谱进行了研究。作为三齿配体，已经使用了双（2-二苯基膦基乙基）苯基膦（dpepp）。三种不同的双齿配体是1,2-双（二乙基膦基）乙烷（depe），1,2-双（二苯基膦基）乙烷（dppe）和R-（+）-1,2-双（二苯基膦基）丙烷（1 ，2-dppp）。根据配合物的几何和电子结构，可以识别和解释NN以及1-3的金属N振动。记录并完全分析了（31）P NMR光谱。而且，进行相关光谱（COSY）-45测量以确定耦合常数的相对符号。特别注意针对不同异构体及其（31）P NMR的检测，以及振动光谱性质。讨论了该结果对于用膦配合物固定合成氮的面积的影响。
• Bonding, activation, and protonation of dinitrogen on a molybdenum pentaphosphine complex — Comparison to <i>trans</i>-bis(dinitrogen) and -nitrile – dinitrogen complexes with tetraphosphine coordination
  作者：Gerald C Stephan、Gerhard Peters、Nicolai Lehnert、Carsten M Habeck、Christian Näther、F Tuczek

  DOI：10.1139/v05-015

  日期：2005.4.1

  The molybdenum-N₂ pentaphosphine complex [Mo(N₂)(dpepp)(dppm)] (1) containing a bi- and a tridentate phosphine ligand (dpepp = PhP(CH₂CH₂PPh₂)₂, dppm = Ph₂PCH₂PPh₂) has been prepared and characterized. By protonation of 1 with triflic acid the NNH₂ complex [Mo(NNH₂)(dpepp)(dppm)](CF₃SO₃)₂ (2) is formed without loss of the pentaphosphine coordination. The electronic properties of 1 and 2 and their ¹⁵N and (or) ²H counterparts are investigated by NMR, IR, and Raman spectroscopy coupled to DFT frequency and NMR shift calculations. Force constants are evaluated from experimental frequencies and isotope shifts by the quantum chemistry based normal coordinate analysis procedure (QCB-NCA). The results for the N₂ complex 1 are compared with those obtained earlier for bis(dinitrogen) and trans-nitrile dinitrogen systems. Importantly, the N₂ in the pentaphosphine complex is more strongly activated compared to corresponding bis(dinitrogen) compounds and more weakly activated compared to trans-nitrile N₂ systems. The activation of the NNH₂ ligand in complex 2 is similar to trans-nitrile systems and weaker compared to corresponding NNH₂ complexes with coordinated anions like [MoF(NNH₂)(dppe)₂](BF₄). These results are discussed based on the relative donor–acceptor properties of the respective trans ligands, demonstrating the influence of σ donation and π acceptance on the activation of N₂ in transition metal complexes.Key words: nitrogen fixation, phosphine complexes, NMR shifts, DFT calculations, normal coordinate analysis.

  钼-N2五磷配合物[Mo(N2)(dpepp)(dppm)](1)，包含一个双齿和一个三齿膦配体(dpepp = PhP(CH2CH2PPh2)2，dppm = Ph2PCH2PPh2)，已被制备和表征。通过三氟甲磺酸质子化1，形成NNH2配合物[Mo(NNH2)(dpepp)(dppm)](CF3SO3)2(2)，而不失去五磷配位。通过核磁共振( NMR )、红外( IR )和拉曼光谱学，结合DFT频率和NMR位移计算，研究了1和2及其15N和(或)2H对应物的电子性质。通过基于量子化学的正常坐标分析过程(QCB-NCA)从实验频率和同位素位移中评估力常数。将N2配合物1的结果与先前获得的双(二氮)和顺式-腈二氮系统进行比较。重要的是，与相应的双(二氮)化合物相比，五磷配合物中的N2更强烈活化，而与顺式-腈N2系统相比则更弱。复合物2中NNH2配体的活化类似于顺式-腈系统，并且与配位阴离子的相应NNH2配合物[MoF(NNH2)(dppe)2](BF4)相比更弱。这些结果基于相应顺式配体的相对给体-受体性质进行讨论，证明了σ捐赠和π受体对过渡金属配合物中N2的活化的影响。关键词：氮固定，膦配合物，NMR位移，DFT计算，正常坐标分析。
• Reactions of coordinated dinitrogen. 8. Formation of ammonia by protonation of a molybdenum-dinitrogen complex and isolation and characterization of the molybdenum-containing product
  作者：John A. Baumann、T. Adrian George

  DOI：10.1021/ja00539a035

  日期：1980.9

  This is the first reported conversion of metal-coordinated dinitrogen into ammonia in which the fate of the metal has been determined. This reaction is shown in the following equation, where triphos = PhP(CH/sub 2/CH/sub 2/PPh/sub 2/)/sub 2/ and L = PPh/sub 3/:2Mo(N/sub 2/)/sub 2/(triphos)(L) + 8HBr ..-->.. 2NH/sub 4/Br + 2MoBr/sub 3/(triphos) + 3N/sub 2/ + 2L. The metal complex which is a new subclass

  这是首次报道的金属配位二氮转化为氨，其中金属的归宿已被确定。该反应如下式所示，其中 triphos = PhP(CH/sub 2/CH/sub 2/PPh/sub 2/)/sub 2/ 和 L = PPh/sub 3/:2Mo(N/sub 2/ )/sub 2/(triphos)(L) + 8HBr ..-->.. 2NH/sub 4/Br + 2MoBr/sub 3/(triphos) + 3N/sub 2/ + 2L。金属络合物是钼的双（二氮）络合物的新亚类，在四氢呋喃（THF）溶液中与无水溴化氢反应生成溴化铵。在反应产物中没有检测到肼或溴化肼。在真空除去溶剂和过量的HBr后，通过红外光谱检测反应产物中的溴化铵。氨的产率通过水、非水（乙醇）或两相（二氯甲烷-水）萃取残留物中的溴化铵后，通过吲哚酚法定量测定。含钼产物在二氯甲烷-水萃取步骤中缓慢分解。在单独的实验中进行纯 MoBr/sub