triphenylphosphinemolybdenumpentacarbonyl | 14971-42-7

• 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: triphenylphosphinemolybdenumpentacarbonyl
• 英文别名: triphenylphosphine molybdenum pentacarbonyl；Carbon monoxide;molybdenum;triphenylphosphane
• CAS: 14971-42-7
• 化学式: C₂₃H₁₅MoO₅P
• 分子量: 498.283
• InChiKey: JVHVYVWAJRLHIO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.25
• 重原子数：
  30
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  triphenylphosphinemolybdenumpentacarbonyl 、 N,N'-bis-(4-methylbenzylidene)-1,2-propanediamine 以 苯 为溶剂， 以78.8%的产率得到μ-(N,N'-bis(4-methylbenzylidene)-1,2-propanediamine)octacarbonylbis(triphenylphosphine)dimolybdenum(0)
  参考文献：
  名称：

  Aldimine derivatives of molybdenum carbonyl

  摘要：

  Aldimines (Ald) such as N,N'-bis(4-methylbenzylidene)-1,2-propanediamine (Ald1), N,N'-bis(4-methoxybenzylidene)-1,2-propanediamine (Ald2) or N,N'-bis(4-N,N-dimethylaminobenzylidene)-1,2-propanediamine (Ald3) reacted with MO(CO)6 to give the respective cis-[(Ald)Mo(CO)4] complexes. N,N'-bis-(4-N,N-dimethylaminobenzylidene)1,3-propanediamine, in spite of comparatively poor reactivity, gave analogous tetracarbonyl, but its 1,4-butanediamine and 1,6-hexanediamine analogues did not give similar derivatives. Ald1-Ald3 after reaction with [(Ph3P)Mo(CO)5] gave corresponding aldimine bridged dinuclear [(Ph3P)(CO)4Mo(mu-Ald)Mo(CO)4(Ph3P)]. Cis-[(Ald)Mo(CO)4] gave [(Ald) Mo(CO)3X2] when reacted with X2 (X = Br or I), but produced [(Ald)MoCl4] after reaction with chlorine. NO reacted with tetracarbonyls to yield a mixture of unusual [(NO)(Ald) MO(CO)2(NO2)] and [(NO)2(Ald)Mo(NO2)2], but NOCl yielded only [(Ald) MO(CO)2(NO)Cl].

  DOI：

  10.1016/s0277-5387(00)83018-1
• 作为产物：
  描述：

  cis-{molybdenum(0)(carbonyl)4(P(phenyl)3)2} 在 CO 作用下， 以 四氯乙烯 为溶剂， 生成 triphenylphosphinemolybdenumpentacarbonyl
  参考文献：
  名称：

  Steric contributions to the solid-state structures of bis(phosphine) derivatives of molybdenum carbonyl. X-ray structural studies of cis-Mo(CO)4[PPh3-nMen]2 (n = 0, 1, 2)

  摘要：

  DOI：

  10.1021/ic00131a055

文献信息

• Organometallic chemistry in a conventional microwave oven: the facile synthesis of group 6 carbonyl complexes
  作者：Michael Ardon、Graeme Hogarth、Daniel T.W Oscroft

  DOI：10.1016/j.jorganchem.2004.04.030

  日期：2004.8

  however, this reaction requires an inert atmosphere. While W(CO)6 reacts rapidly with amines to give cis diamine adducts in high yields, direct reactions with phosphines are not so clean. Bis(phosphine) complexes are, however, cleanly formed when a small amount of piperidine is added to the reaction mixture, presumably via the bis(piperidine) complex cis-[W(CO)4(pip)2]. Reactions with Cr(CO)6 generally

  通过在改进的常规微波炉中进行反应，可以改善，加速和简化通过回流进行的合成。为了证明这种方法的潜力，据报道合成了20多种第6组有机金属化合物。六羰基，最著名的是Mo（CO）6，在改良的常规微波炉中与一定范围的单，双和三齿配体反应。它们通常在没有惰性气氛的情况下进行，产率高且反应时间短。例如，在20分钟内以大于95％的收率制备顺式[[Mo（CO）4（dppe）]。Mo（CO）6与二环戊二烯的反应可简单地一步合成[CpMo（CO）3 ]。2个在> 90％的产率，这与在甲苯中的炔烃以产生dimetallatetrahedrane衍生物进一步反应，混合[Cp 2沫2（CO）4（μ-RC 2 R）]; 大概是通过原位形成对空气敏感的[CpMo（CO）2 ] 2来实现的。还可以在45分钟内以48％的收率制备四乙酸二钼酸乙酯，但是，该反应需要惰性气氛。W（CO）6与胺快速反应以高产率生成顺式二胺加合物，但
• Rearrangement of Metallabenzynes to Chlorocyclopentadienyl Complexes
  作者：Jiangxi Chen、Ka-Ho Lee、Tingbin Wen、Feng Gao、Herman H. Y. Sung、Ian D. Williams、Zhenyang Lin、Guochen Jia

  DOI：10.1021/om501181u

  日期：2015.3.9

  formed by a migratory insertion reaction of the osmabenzyne complex Os≡C-C(SiMe3)═C(CH3)-C(SiMe3)═CH}Cl2(CO)(PPh3). DFT calculations show that the relative thermal stability of metallabenzynes Os(≡C-CH═CHCH═CH)Cl2(L)2 and the corresponding isomeric carbene complexes Os═C(−CH═CHCH═CH−)}Cl2(L)2 as well as the chlorocyclopentadienyl complexes Os(η5-C5ClH4)Cl(L)2 (L = CO, phosphine, pyridine, amine) is strongly

  所述osmabenzyne复杂O的治疗≡CC（森达3）= C（CH 3）-C（森达3）= CH-}氯2（PPH 3）2用的Mo（CO）6在回流的苯中产生的η 5 - chlorocyclopentadienyl复杂操作系统η 5 -C 5的HCl（CH 3）（森达3）2 }氯（CO）（PPH 3）和Mo（CO）5（PPH 3）。计算研究表明，氯环戊二烯基络合物最可能是通过卡宾中间体Os ═C（C（SiMe 3）═C（CH 3）-C（SiMe）生成的3）═CH-）} Cl 2（CO）（PPh 3），是由苯并吲哚配合物Os ≡CC（SiMe 3）═C（CH 3）-C（SiMe 3）═CH} Cl的迁移插入反应形成的2（CO）（PPh 3）。DFT计算表明，金属氧合酶Os（≡C-CH═CHCH═CH）Cl 2（L）2和相应的异构卡宾配合物Os ═C（-CH═CHCH═CH-）} Cl 2（
• Sonochemistry and sonocatalysis of metal carbonyls
  作者：Kenneth S. Suslick、James W. Goodale、Paul F. Schubert、Hau H. Wang

  DOI：10.1021/ja00356a014

  日期：1983.9

  67 The labeled precursor utilized in the present investigation, 1-deoxy-D-three [ l-2H3,5-2Hl]pentulose (6) was synthesized from 2,4-O-benzylidene-~-[4-~H~] threose, which is available from D[ l-2Hl]arabinitol by standard Reaction of the threose derivative with trideuteriomethylmagnesium iodide in ether then gave a mixture of protected, epimeric pentane tetrols, which was oxidized by the stannylene

  然后提取硫胺素，并用亚硫酸氢盐裂解，以通常的方式得到 HET。将其转化为三氟乙酸酯用于 MS 检查。
• ³¹P chemical shift anisotropies of trimethyl- and triphenylphosphine-substituted Group 6 metal pentacarbonyl complexes
  作者：Jordan H Wosnick、Frederick G Morin、Denis FR Gilson

  DOI：10.1139/v98-167

  日期：1998.9.1

  The ³¹P chemical shift tensor components and anisotropies of the trimethyl- and triphenylphosphine complexes of the group 6 metal pentacarbonyls, M(CO)₅PR₃ (M = Cr, Mo, W and R = Me, Ph), have been measured using solid-state CP-MAS ³¹P NMR spectroscopy. For the trimethylphosphine derivatives, the chemical shift tensors have near axial symmetry and the shift tensor components are in reasonable agreement with the calculated values for the chromium and molybdenum complexes. In the triphenylphosphine complexes, the tensors are asymmetric due to the different torsion angles of the phenyl rings. The trend to higher shielding of the isotropic ³¹P chemical shifts on descending group 6 arises from changes in the perpendicular components of the shift tensor. The one-bond coupling constants, ¹J(^95/97Mo-³¹P), for the trimethyl- and triphenylphosphine complexes are 129 and 133 Hz, respectively.Key words: chemical shift anisotropy, phosphines, chromium, molybdenum, tungsten.

  三甲基和三苯基膦配合物的31P化学位移张量分量和各向异性已经使用固体CP-MAS 31P NMR光谱学进行了测量。对于三甲基膦衍生物，化学位移张量具有近轴对称性，并且位移张量分量与铬和钼配合物的计算值基本一致。在三苯基膦配合物中，张量是不对称的，这是由于苯环的扭转角不同。下降到第6族元素时，各向异性31P化学位移的屏蔽趋势是由于位移张量的垂直分量的变化。对于三甲基和三苯基膦配合物的一键耦合常数，1J(95/97Mo-31P)，分别为129和133赫兹。关键词：化学位移各向异性，膦化合物，铬，钼，钨。
• Kinetics and mechanism of oxidative cleavage of the metal-metal bond in [M2(CO)10]2−, MCr, Mo and W
  作者：Julia R. Phillips、William C. Trogler

  DOI：10.1016/s0020-1693(00)92408-3

  日期：1992.8

  Electrochemically-induced metal-metal bond cleavage in [M2(CO)10]2− (MCr, Mo, W) has been studied using cyclic voltammetry, bulk electrolysis and double potential step chronocoulometry. Metal-metal bond homolysis, which occurs on oxidation in THF, can be modeled with an EC second-order disproportionation mechanism. The key step involves reaction of 2[M2(CO)10]·− to form [M2(CO)10]2− and M(CO)5(THF). Electron transfer

  摘要：利用循环伏安法，本体电解法和双电势步计时库仑法研究了[M2（CO）10] 2-（MCr，Mo，W）中电化学诱导的金属-金属键断裂。可以在EC二级歧化机理中模拟在THF中氧化时发生的金属-金属键均质化。关键步骤涉及2 [M2（CO）10] 2-的反应，形成[M2（CO）10] 2-和M（CO）5（THF）。均相歧化步骤的电子传递速率常数kd通过双电势步计时库仑法确定：[W2（CO）10]·-的2.5±0.1×103 M-1 s-1和5.9±0.3×102 M-1在20.0°C下于THF中[Mo2（CO）10]-的s-1。[Cr2（CO）10]·-自由基歧化速度太慢，无法在室温下观察到，但kd⩽1.7×102 M-1 s-1的值估计是速率常数在35时的上限。0°C。确定了kd的激活参数。对于[Mo 2（CO）10]-，ΔH‡＝ 6.9±0.5kcal mol-1，并且ΔS‡＝ -22.4±1