Os3(CO)8(μ3-η2:η2:η2-C6H6)(PPh3) | 121500-40-1

• 英文名称: Os3(CO)8(μ3-η2:η2:η2-C6H6)(PPh3)
• CAS: 121500-40-1
• 化学式: C₃₂H₂₁O₈Os₃P
• 分子量: 1135.09
• InChiKey: OAOOYWGAGDMSPK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  Os3(CO)8(μ3-η2:η2:η2-C6H6)(PPh3) 以 甲苯 为溶剂， 以90%的产率得到H2Os3(CO)8(μ3-η1:η2:η1-C6H4)PPh3
  参考文献：
  名称：

  苯三os簇合物的光异构化：平坦金属表面上的芳烃活化模型

  摘要：

  羰基tri络合物中表面封端的苯配体的光诱导双金属化作用是作为簇类似物的，用于过渡金属表面吸附剂覆盖层中苯的活化。

  DOI：

  10.1039/c39880001071
• 作为产物：
  描述：

  {Os3(CO)8(NCCH3)(μ3:η2:η2:η2-C6H6)} 在 P(C₆H₅)3 作用下， 以 二氯甲烷 为溶剂， 以93%的产率得到Os3(CO)8(μ3-η2:η2:η2-C6H6)(PPh3)
  参考文献：
  名称：

  A face-capping bonding mode for benzene in triosmium carbonyl cluster complexes

  摘要：

  This paper describes the synthesis of trinuclear metal complexes containing benzene in a new face-capping bonding mode, (mu-3:eta-2:eta-2:eta-2-C6H6), that accurately models the coordination geometry of benzene chemisorbed nondissociatively on the surface of a close-packed metal lattice. [Os3(CO)9(mu-3:eta-2:eta-2:eta-2-C6H6)] (1), the parent complex, is elaborated through stepwise "dehydrogenation" of the triply-bridging cyclohexadienyl compound [(mu-H)Os3(CO)9(mu-3:eta-2:eta-1:eta-2-C6H7)], and an X-ray diffraction analysis reveals intriguing multiple bond fixation within the coordinated arene: Im, a = 8.412 (i) angstrom, b = 35.449 (4) angstrom, c = 8.877 (1) angstrom, beta = 92.44 (1)-degrees, V = 2644.7 angstrom3, Z = 6, R = 3.2%, R(w) = 3.4% for 2465 reflections with F(o) > 4-sigma(F(o)). The ring symmetrically caps a trimetal face and shows Kekule-type distortion toward the hypothetical cyclohexa-1,3,5-triene (on average, C-C bond lengths alternate between 1.41 (3) and 1.51 (4) angstrom). The preparation of an analogous toluene complex, [Os3(CO)9(mu-3:eta-2:eta-2:eta-2-C6H5Me)] is also reported. Oxidative decarbonylation of 1 by trimethylamine N-oxide in the presence of MeCN affords the lightly-ligated complex [Os3(CO)8(NCMe)(mu-3:eta-2:eta-2:eta-2-C6H6)] (9). Two-electron donor ligands (e.g., CO, PR3, C5H5N, olefins) readily displace the labile nitrile ligand from 9, giving derivatives [OS3(CO)8(L)(mu-3:eta-2:eta-2:eta-2-C6H6)] that retain the face-capping benzene moiety. The molecular structures of [OS3(CO)8(PPh3)(mu-3:eta-2:eta-2:eta-2-C6H6)] and [Os3-(CO)9(eta-2-CH2CH2)(mu-3:eta-2:eta-2:eta-2-C6H6)] been determined by X-ray crystallography and are derived from that of complex 1, with an equatorial carbonyl ligand being replaced by triphenylphosphine and a pi-bound ethylene ligand, respectively. The Cluster [Os3(CO)8(PPh3)(mu-3:eta-2:eta-2:eta-2-C6H6] crystallizes in space group P2(1)/c with a = 13.381 (5) angstrom, b = 14.894 (5), c = 16.896 (7) angstrom, beta = 113.33 (3)-degrees, V = 3092.0 angstrom3, Z = 4, R = 3.9%, R(w) = 4. 1 % for 4747 reflections with F(o) > 4-sigma(F(o)). The cluster [Os3(CO)8(eta-2-CH2CH2)(mu-3:eta-2:eta-2:eta-2:-C6H6)] crystallizes in space group P2(1)/n with a = 8.876 (1) angstrom, b = 14.665 (2) angstrom, c = 14.178 (2) angstrom, beta = 92.56 (2)-degrees, V = 1843.7 angstrom3, Z = 4, R = 4.8%, R(w) = 4.8% for 1890 reflections with F(o) > 4-sigma(F(o)). Semiempirical molecular orbital calculations provide useful insights into the structure and bonding of complex 1. Primary contributions to metal-arene bonding arise from overlap of the benzene HOMO with the LUMO of the cluster fragment and through pi-back donation to the benzene LUMO from a high-lying cluster-based molecular orbital. The trigonal ring distortion may be traced to an internal mixing of the benzene pi-system that leads to increased overlap in the C-C bonds eclipsing the metal atoms, at the expense of the alternate noneclipsing bonds which consequently become elongated. Possible relationships between these compounds and aromatic adsorbate complexes of transition metal surfaces are also explored.

  DOI：

  10.1021/ja00033a026