Os3(CO)9(μ3-η2:η2:η2-C6H6) | 111045-40-0

• 英文名称: Os3(CO)9(μ3-η2:η2:η2-C6H6)
• CAS: 111045-40-0
• 化学式: C₁₅H₆O₉Os₃
• 分子量: 900.807
• InChiKey: YZZIAGIZQOFYNY-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)9(μ3-η2:η2:η2-C6H6) 以 甲苯 为溶剂， 以>99的产率得到1,1,1,2,2,2,3,3,3-nonacarbonyl-1,2:2,3-μ-dihydrido-μ3-o-phenylene-triangulo-triosmium
  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：

  在 [CPh₃][BF₄] 、 1,8-diazabicyclo[5.4.0]undec-7-ene 作用下， 以 not given 为溶剂， 生成 Os3(CO)9(μ3-η2:η2:η2-C6H6)
  参考文献：
  名称：

  苯在一个新面孔封盖的键合方式：的分子结构的[Ru 6 C（CO）11（μ 3 -η 2：η 2：η 2 -C 6 H ^ 6）（η 6 -C 6 H ^ 6）]和[O的3（CO）9（μ 3 -η 2：η 2：η 2 -C 6 H ^ 6）]

  摘要：

  在簇络合物苯配体，其中所述环被对称地放置上方的金属三角形的新的协调模式已建立晶体在羰基配合物的[Ru 6 C（CO）11（μ 3 -η 2：η 2： η 2 -C 6 H ^ 6）（η 6 -C 6 H ^ 6）]和[O的3（CO）9（μ 3 -η 2：η 2：η 2 -C 6 H ^ 6）。

  DOI：

  10.1039/c39850001682

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。
• Synthesis and molecular structure of the novel triosmium bis(benzene) cluster [Os₃(CO)₆(η⁶-C₆H₆)(µ₃: η²:η²: η²-C₆H₆]
  作者：Scott L. Ingham、Brian F. G. Johnson、Jacqueline G. M. Nairn

  DOI：10.1039/c39950000189

  日期：——

  The novel bis(benzene) complex [Os3(CO)6(µ3: η2:η2: η2-C6H6)(η6-C6H6)] is prepared and characterised by single-crystal X-ray analysis; the cluster exhibits two distinct coordination modes of benzene, one terminally bound in an η6 manner, the other in a µ3 face-capping coordination mode.

  该新型双（苯）配合物[O的3（CO）6（μ 3：η 2：η 2：η 2 -C 6 H ^ 6）（η 6 -C 6 H ^ 6）]的制备和表征由单晶X射线分析；簇显示出苯的两种不同的配位模式，一个在一个末端η绑定6在μ的方式，其他3面封盖的配位模式。
• 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)]
  作者：Mark A. Gallop、Brian F. G. Johnson、Jack Lewis、Paul R. Raithby

  DOI：10.1039/c39870001809

  日期：——

  The cluster-alkene complexes [Os3(CO)8(η2-CH2CHR)(µ3-η2:η2:η2-C6H6)](RH, Ph) contain benzene ligands in a face-capping co-ordination mode, and the geometry of the ethylene derivative has been confirmed by a single-crystal X-ray analysis; the intramolecular dynamics of these complexes have been investigated in solution by n.m.r. spectroscopy and are discussed in terms of arene ring-whizzing and alkene rotation.

  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。
• A face-capping bonding mode for benzene in triosmium carbonyl cluster complexes
  作者：Mark A. Gallop、M. Pilar Gomez-Sal、Catherine E. Housecroft、Brian F. G. Johnson、Jack Lewis、Steven M. Owen、Paul R. Raithby、Anthony H. Wright

  DOI：10.1021/ja00033a026

  日期：1992.3

  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.
• Gallop, Mark A.; Johnson, Brian F. G.; Lewis, Jack, Journal of the Chemical Society, Dalton Transactions, 1989, p. 481 - 488
  作者：Gallop, Mark A.、Johnson, Brian F. G.、Lewis, Jack、Wright, Anthony H.

  DOI：——

  日期：——