bis-μ-dimethylphosphido-octacarbonyldimolybdenum (Mo-Mo)

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: bis-μ-dimethylphosphido-octacarbonyldimolybdenum (Mo-Mo)
• 英文别名: [(CO)4Mo(μ-PMe2)2Mo(CO)4]
• 化学式: C₁₂H₁₂Mo₂O₈P₂
• 分子量: 538.05
• InChiKey: KUBJZDKJVUJKTP-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：

  bis-μ-dimethylphosphido-octacarbonyldimolybdenum (Mo-Mo) 、 三丁基膦 以 萘烷 为溶剂， 生成
  参考文献：
  名称：

  七配位化合物双-μ-二苯基膦基和双-μ-二甲基膦基-八羰基二钼钼（MoMo）与三正丁基膦反应的动力学和取代机理

  摘要：

  摘要双核磷桥联钼配合物[（CO）4 Mo（μ-PR2）2 M o（CO）4]（R = Ph或Me）与P（n-Bu）3反应生成相应的单双膦衍生物。萘烷中第一个取代的动力学研究表明，CO分解机理涉及配位不饱和中间体[（CO 4）Mo（μ-PR2）2 M o（CO）3]。总的取代率取决于CO离解率k 1，以及取决于CO，k -1和P（n-Bu）3，k 2对反应中间体的双分子进攻的速率。磷桥处的取代基的性质显着影响k 1的值，与甲基相比，苯基的k 1值更高。这主要是由于较低的活化焓（ΔH 1 * = 125（Ph）相对于141（Me）kJ mol -1），这可能反映了在反位存在更多吸电子配体的情况下MoCO键的弱化。竞争率比率k -1 / k 2的值始终始终大于1，这表明相对于较大的P（n-Bu）3而言，较小的CO的攻击更为有利。这表明在起始的七坐标配合物的分子结构上观察到的空间拥挤也应在其六坐标中间体的反应性上起重要作用。

  DOI：

  10.1016/s0020-1693(01)00521-7
• 作为产物：
  描述：

  [NEt4][W(CO)5I] 、 [NEt₄][Mo(CO)₅I] 、 1,1,2,2-四甲基-二膦 在 AgBF₄ 作用下， 以 四氢呋喃 为溶剂， 生成 bis-μ-dimethylphosphido-octacarbonyldimolybdenum (Mo-Mo) 、 [(CO)4W(μ-PMe2)2W(CO)4] 、 [(CO)4Mo(μ-PMe2)2W(CO)4]
  参考文献：
  名称：

  Improved synthesis of the heteronuclear phosphido Mo–W complex and its use as MOCVD precursor

  摘要：

  The heteronuclear complex [(Co)(4)Mo(mu -PMe2)(2)W(CO)(4)] (1) has been prepared by thermal cyclization of the linear dimer [(CO)(5)MoPMe2PMe2W(CO)(5)]. An improved yield in 1, with respect to the literature, has been obtained with a different synthetic route to the linear complex and with a better separation, by flash chromatography, of 1 from its homonuclear Mo-Mo and W-W congeners. The conditions of thermal cyclization are rather critical and in one case the major product was the phosphine complex [M(mu -PMe2)(CO)(3)(PMe3)](2) (M = Mo and W in 1/4 ratio: monoclinic, space group P2(1)/n, a = 9.568(1), b = 9.305(1), c = 15.009(2) Angstrom, beta = 102.3(1)degrees, Z = 2, R = 0.035, R-w = 0.036). Complex 1 is a convenient MOCVD precursor and sublimes at low temperatures, less than or equal to 85 degreesC, to give thin films of mixed MoO3/WO3 oxides or Mo/W alloys, depending on the deposition conditions. (C) 2001 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(01)00603-x

文献信息

• Trenkle, Armin; Vahrenkamp, Heinrich, Chemische Berichte, 1981, vol. 114, # 4, p. 1366 - 1381
  作者：Trenkle, Armin、Vahrenkamp, Heinrich

  DOI：——

  日期：——
• Improved synthesis of the heteronuclear phosphido Mo–W complex and its use as MOCVD precursor
  作者：Marino Basato、Enrico Brescacin、Eugenio Tondello、Giovanni Valle

  DOI：10.1016/s0020-1693(01)00603-x

  日期：2001.10

  The heteronuclear complex [(Co)(4)Mo(mu -PMe2)(2)W(CO)(4)] (1) has been prepared by thermal cyclization of the linear dimer [(CO)(5)MoPMe2PMe2W(CO)(5)]. An improved yield in 1, with respect to the literature, has been obtained with a different synthetic route to the linear complex and with a better separation, by flash chromatography, of 1 from its homonuclear Mo-Mo and W-W congeners. The conditions of thermal cyclization are rather critical and in one case the major product was the phosphine complex [M(mu -PMe2)(CO)(3)(PMe3)](2) (M = Mo and W in 1/4 ratio: monoclinic, space group P2(1)/n, a = 9.568(1), b = 9.305(1), c = 15.009(2) Angstrom, beta = 102.3(1)degrees, Z = 2, R = 0.035, R-w = 0.036). Complex 1 is a convenient MOCVD precursor and sublimes at low temperatures, less than or equal to 85 degreesC, to give thin films of mixed MoO3/WO3 oxides or Mo/W alloys, depending on the deposition conditions. (C) 2001 Elsevier Science B.V. All rights reserved.
• Kinetics and substitution mechanism in the reaction of the seven-coordinate complexes bis-μ-diphenylphosphido- and bis-μ-dimethylphosphido-octacarbonyldimolybdenum (MoMo) with tri-n-butyl-phosphine
  作者：Marino Basato

  DOI：10.1016/s0020-1693(01)00521-7

  日期：2001.9

  The dinuclear phosphido-bridged molybdenum complexes [(CO) 4 Mo(μ-PR 2 ) 2 M o(CO) 4 ] (R=Ph or Me) react with P(n-Bu) 3 to give the corresponding mono and bis-phosphine derivatives. A kinetic study of the first substitution in decalin indicates a CO-dissociative mechanism involving the coordinatively unsaturated intermediate [(CO 4 ) Mo(μ-PR 2 ) 2 M o(CO) 3 ]. The overall substitution rate depends on

  摘要双核磷桥联钼配合物[（CO）4 Mo（μ-PR2）2 M o（CO）4]（R = Ph或Me）与P（n-Bu）3反应生成相应的单双膦衍生物。萘烷中第一个取代的动力学研究表明，CO分解机理涉及配位不饱和中间体[（CO 4）Mo（μ-PR2）2 M o（CO）3]。总的取代率取决于CO离解率k 1，以及取决于CO，k -1和P（n-Bu）3，k 2对反应中间体的双分子进攻的速率。磷桥处的取代基的性质显着影响k 1的值，与甲基相比，苯基的k 1值更高。这主要是由于较低的活化焓（ΔH 1 * = 125（Ph）相对于141（Me）kJ mol -1），这可能反映了在反位存在更多吸电子配体的情况下MoCO键的弱化。竞争率比率k -1 / k 2的值始终始终大于1，这表明相对于较大的P（n-Bu）3而言，较小的CO的攻击更为有利。这表明在起始的七坐标配合物的分子结构上观察到的空间拥挤也应在其六坐标中间体的反应性上起重要作用。