{Os3(CO)8(NCCH3)(μ3:η2:η2:η2-C6H6)} | 139344-76-6

• 英文名称: {Os3(CO)8(NCCH3)(μ3:η2:η2:η2-C6H6)}
• CAS: 139344-76-6
• 化学式: C₁₆H₉NO₈Os₃
• 分子量: 913.849
• InChiKey: MDLSGXQMAWJVKE-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：

  {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
• 作为产物：
  描述：

  Os3(CO)9(μ3-η2:η2:η2-C6H6) 、 乙腈 在 trimethylamine N-oxide 作用下， 以 乙腈 为溶剂， 生成 {Os3(CO)8(NCCH3)(μ3:η2:η2:η2-C6H6)}
  参考文献：
  名称：

  Organometallic ‘helicopters.’ Characterisation of the non-rigid triosmium arene–alkene complexes [Os₃(CO)₈(η²-CH₂CHR)(µ₃-η²:η²:η²-C₆H₆)], (RH, Ph) and the X-ray crystal structure of [Os₃(CO)₈(η²-CH₂CH₂)(µ_3-η²:η²:η²-C₆H₆)]

  摘要：

  簇烯烃配合物 [Os3(CO)8(δ2-CH2CHR)(µ3-δ2:δ2:δ2-C6H6)](RH, Ph) 在面封端 co 中含有苯配体-配位模式，乙烯衍生物的几何形状已通过单晶X射线分析得到证实；这些复合物的分子内动力学已通过核磁共振在溶液中进行了研究。光谱并根据芳环旋动和烯烃旋转进行了讨论。

  DOI：

  10.1039/c39870001809

文献信息

• Benzene migration in an osmium cluster: the formation of Os₃(CO)₇(η⁶-C₆H₆)(µ₃: η¹: η²: η¹-C₂Me₂) from Os₃(CO)₉(µ₃: η²: η²: η²-C₆H₆). The crystal structure of Os₃(CO)₇(η⁶-C₆H₆)(µ₃: η¹: η²: η¹-C₂Me₂)
  作者：Dario Braga、Fabrizia Grepioni、Brian F. G. Johnson、Jack Lewis、Marcia Martinelli、Mark A. Gallop

  DOI：10.1039/c39900000053

  日期：——

  The activated cluster [Os3(CO)7(C2H4)(µ3 : η2 : η2 : η2-C6H6)(MeCN)] reacts with alkynes RC2R′(R = R′= H, Ph or Me; R = H, R′= Ph; R = ME, R′= Et), to produce the new clusters [OS3(CO)7(η6-C6H6)(µ3 : η1 : η2 : η1-RC2R′)] in which the benzene is bonded to a single metal atom as shown by a single crystal X-ray structure determination of the C2Me2 derivative.

  活化簇[O的3（CO）7（C 2 H ^ 4）（μ 3：η 2：η 2：η 2 -C 6 H ^ 6）（MeCN中）]与炔发生反应RC 2 R'（R = R' = H中，Ph或Me; R = H，R'=苯基; R = Me，R'= ET），以产生新的簇[OS 3（CO）7（η 6 -C 6 H ^ 6）（μ 3：η 1：η 2：η 1 -RC 2R'）]，其中苯与单金属原子键合，如C 2 Me 2衍生物的单晶X射线结构测定所示。