trans-bis(2,6-bis(2,6-diisopropylphenyl)phenylisocyanido)tetracarbonylmolybdenum | 1185931-37-6

• 英文名称: trans-bis(2,6-bis(2,6-diisopropylphenyl)phenylisocyanido)tetracarbonylmolybdenum
• 英文别名: trans-[Mo(CO)4(CNC6H3(C6H3iPr2-2,6)2-2,6)2]
• CAS: 1185931-37-6
• 化学式: C₆₆H₇₄MoN₂O₄
• 分子量: 1055.26
• InChiKey: MXRWURKXHPUDSW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  [MoI2(CO)2(CNC6H3(C6H3iPr2-2,6)2-2,6)2] 以 not given 为溶剂， 生成 trans-bis(2,6-bis(2,6-diisopropylphenyl)phenylisocyanido)tetracarbonylmolybdenum
  参考文献：
  名称：

  氧化脱羰米钼的三联苯异腈配合物和钨：前体低坐标异腈配合

  摘要：

  合成的研究都寻址钼的氧化脱羰和由拖累支持钨络合物米三联苯胩配体CNAR Dipp2（AR Dipp2 = 2,6-（2,6-（我-Pr）2 C ^ 6 ħ 3）2 C ^ 6 H 3）。这些研究代表了努力获取卤化物或拟卤化物M / CNAr Dipp2物种（M = Mo，W）用作低配位，低价6族异氰酸酯络合物的前体的努力。四-和三羰基钨配合物反式W（CO）4（CNAr ）的合成和结构化学报告了Dipp2）2和反式W（NCMe）（CO）3（CNAr Dipp2）2。乙腈加合物反式M（NCMe）（CO）3（CNAr Dipp2）2（M = Mo，W）与I 2反应形成二价二碘化物络合物，其中Mo和W之间的脱羰程度不同。例如，生成了二碘化物，二羰基络合物MoI 2（CO）2（CNAr Dipp2）2，该二碘化物在溶液中具有S = 1的基态。顺磁性6 MX 2 L组很少有4种配合物，并且针对其他抗磁性和C

  DOI：

  10.1021/ic2015868

文献信息

• Effective Control of Ligation and Geometric Isomerism: Direct Comparison of Steric Properties Associated with Bis-mesityl and Bis-diisopropylphenyl <i>m</i>-Terphenyl Isocyanides
  作者：Treffly B. Ditri、Brian J. Fox、Curtis E. Moore、Arnold L. Rheingold、Joshua S. Figueroa

  DOI：10.1021/ic9010828

  日期：2009.9.7

  A synthetic procedure for the sterically encumbered m-terphenyl isocyanide CNArDipp2 (Dipp = 2,6-diisopropylphenyl) is presented. In comparison to the less encumbering m-terphenyl isocyanide ligand CNArMes2, the steric attributes of the flanking Dipp groups effectively control the extent of CNArDipp2 ligation to monovalent Cu and Ag centers and zerovalent Mo centers. Direct structural comparisons of Cu(I) and Ag(I) complexes of both CNArDipp2 and CNArMes2 are made. It was found that only two CNArDipp2 ligands are accommodated by monovalent Cu and Ag centers, whereas three CNArMes2 units can readily bind. As demonstrated by both H-1 NMR and FTIR spectroscopic studies, addition of a third equivalent of CNArDipp2 to [(THF)(2)Cu(CNArDipp2)(2)]OTf in C6D6 solution results in slow isocyanide exchange. However, rapid isocyanide exchange is observed when an additional equivalent of CNArDipp2 is added to (TfO)Ag(CNArDipp2)(2). Three CNArMes2 ligands react smoothly with fac-Mo(CO)(3)(NCMe)(3) to afford the octahedral complex fac-Mo(CO)(3)(CNArMes2)(3) which can be converted irreversibly to the mer isomer upon heating in solution. Contrastingly, addition of CNArDipp2 to fac-Mo(CO)(3)(NCMe)(3) results in a mixture of both the tetracarbonyl and the tricarbonyl complexes trans-Mo(CO)(4)(CNArDipp2)(2) and trans-Mo(NCMe)(CO)(3)(CNArDipp2)(2), respectively, in which the encumbering CNArDipp2 ligands are in a traps-disposition. ultraviolet irradiation of the preceding mixture in NCMe/Et2O under an argon flow provides exclusively the tricarbonyl complex trans-Mo(NCMe)(CO)(3)(CNArDipp2)(2). Addition of free CNArDipp2 to trans-Mo(NCMe)(CO)(3)(CNArDipp2)(2) does not result in the binding of a third isocyanide unit by the Mo center as determined by H-1 NMR spectroscopy. Treatment of trans-Mo(NCMe)(CO)(3)(CNArDipp2)(2) with the Lewis base pyridine (py) affords the complex fac,cis-Mo(py)(CO)(3)(CNArDipp2)(2) as determined by X-ray diffraction. Notably, the encumbering nature of the CNArDipp2 units forces a cis C-iso-Mo-C-iso angle of about 100 degrees.