[Cr(CO)2(η2-C6H6)] | 68006-17-7

• 英文名称: [Cr(CO)2(η2-C6H6)]
• 英文别名: (η-benzene)dicarbonylchromium；dicarbonyl-η-benzenechromium；benzene chromium dicarbonyl；(η(6)-C6H6)Cr(CO)2；(η6-C6H6)Cr(CO)2；[(η6-C6H6)(Cr(CO)2)]；[(η6-C6H6)Cr(CO)2]
• CAS: 68006-17-7；697302-49-1
• 化学式: C₈H₆CrO₂
• 分子量: 186.13
• InChiKey: HHDCFTZASWMPHX-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：

  [Cr(CO)2(η2-C6H6)] 在 一氧化碳 作用下， 生成 苯三羰基铬
  参考文献：
  名称：

  UV laser photolysis of (.eta.6-benzene)tricarbonylchromium: time-resolved infrared studies of gas-phase (.eta.6-C6H6)Cr(CO)x (x = 2 and 1)

  摘要：

  The time-resolved infrared absorption spectra of the coordinatively unsaturated (eta(6)-C6H6)Cr(CO)x (x = 2 and 1) species generated via UV laser photolysis of the gas-phase (eta(6)-C6H6)Cr(CO)3 are presented and discussed. The photofragments produced upon 355- and 266-nm photolysis are identified. (eta(6)-C6H6)Cr(CO)2 is the predominant product upon 355-nm photolysis, while both (eta(6)-C6H6)Cr(CO)2 and (eta(6)-C6H6)Cr(CO) are produced upon 266-nm photolysis with a ratio of (eta(6)-C6H6)Cr(CO)2;(eta(6)-C6H6)Cr(CO) of about 2:5. The rate constants for reactions of (eta(6)-C6H6)Cr(CO)2 and (eta(6)-C6H6)Cr(CO) with CO are measured and found to be (6.3 +/- 0.3) x 10(12) and (1.4 +/- 0.2) x 10(12) cm3 mol-1 s-1, respectively. The rate constant for reaction of (eta(6)-C6H6)Cr(CO)2 with CO lies between the corresponding values for spin-allowed and spin-disallowed reactions of other coordinatively unsaturated metal carbonyl species with CO.

  DOI：

  10.1021/j100182a047
• 作为产物：
  描述：

  benzene chromium carbonyl 在 一氧化碳 作用下， 生成 [Cr(CO)2(η2-C6H6)]
  参考文献：
  名称：

  UV laser photolysis of (.eta.6-benzene)tricarbonylchromium: time-resolved infrared studies of gas-phase (.eta.6-C6H6)Cr(CO)x (x = 2 and 1)

  摘要：

  The time-resolved infrared absorption spectra of the coordinatively unsaturated (eta(6)-C6H6)Cr(CO)x (x = 2 and 1) species generated via UV laser photolysis of the gas-phase (eta(6)-C6H6)Cr(CO)3 are presented and discussed. The photofragments produced upon 355- and 266-nm photolysis are identified. (eta(6)-C6H6)Cr(CO)2 is the predominant product upon 355-nm photolysis, while both (eta(6)-C6H6)Cr(CO)2 and (eta(6)-C6H6)Cr(CO) are produced upon 266-nm photolysis with a ratio of (eta(6)-C6H6)Cr(CO)2;(eta(6)-C6H6)Cr(CO) of about 2:5. The rate constants for reactions of (eta(6)-C6H6)Cr(CO)2 and (eta(6)-C6H6)Cr(CO) with CO are measured and found to be (6.3 +/- 0.3) x 10(12) and (1.4 +/- 0.2) x 10(12) cm3 mol-1 s-1, respectively. The rate constant for reaction of (eta(6)-C6H6)Cr(CO)2 with CO lies between the corresponding values for spin-allowed and spin-disallowed reactions of other coordinatively unsaturated metal carbonyl species with CO.

  DOI：

  10.1021/j100182a047

文献信息

• Unusually Slow Photodissociation of CO from (η⁶-C₆H₆)Cr(CO)₃ (M = Cr or Mo): A Time-Resolved Infrared, Matrix Isolation, and DFT Investigation
  作者：Mohammed A. H. Alamiry、Nicola M. Boyle、Christopher M. Brookes、Michael W. George、Conor Long、Peter Portius、Mary T. Pryce、Kate L. Ronayne、Xue-Zhong Sun、Michael Towrie、Khuong Q. Vuong

  DOI：10.1021/om800925s

  日期：2009.3.9

  The photochemistry of (η6-C6H6)M(CO)3 (M = Cr or Mo) is described. Photolysis with λexc. > 300 nm of (η6-C6H6)Cr(CO)3 in low-temperature matrixes containing CO produced the CO-loss product, while lower energy photolysis (λexc. > 400 nm) produced Cr(CO)6. Pulsed photolysis (λexc. = 400 nm) of (η6-C6H6)Cr(CO)3 in n-heptane solution at room temperature produced an excited-state species (1966 and 1888

  的（η光化学6 -C 6 H ^ 6）M（CO）3（M = Cr或Mo）的描述。用λex光解。（η的> 300nm的6 -C 6 H ^ 6）的Cr（CO）3在含CO的低温矩阵产生的CO-损失产物，而较低能量的光解（λ EXC。 > 400纳米）的Cr产生（CO）6。脉冲光解（λ EXC。（η的= 400nm）的6 -C 6 H ^ 6）的Cr（CO）3在Ñ在室温下庚烷溶液产生的激发态物种（1966和1888厘米-1），该衰变超过150个ps至（η 6 -C 6 H ^ 6）的Cr（CO）2（Ñ庚烷）（70％）和（η 6 -C 6 H ^ 6）的Cr（CO）3（30％ ）。脉冲光解（λ 。EXC = 266纳米）的（η 6 -C 6 H ^ 6）的Cr（CO）3在Ñ分配给庚烷产生的条带（η 6 -C 6 H ^ 6）的Cr（CO）2（Ñ -庚烷）（1930和1870 cm -1）在1 ps
• A laser flash photolysis, matrix isolation, and DFT investigation of (η6-C6H5Y)Cr(CO)3 (Y=NH2, OCH3, H, CHO, or CO2CH3)
  作者：Mohammed A.H. Alamiry、Peter Brennan、Conor Long、Mary T. Pryce

  DOI：10.1016/j.jorganchem.2008.06.003

  日期：2008.8

  from (η6-C6H5Y)Cr(CO)3 was measured in 1,1,2-trifluorotrichloroethane (Y = NH2, OCH3, H, CHO, or CO2CH3). Values of 0.24, 0.27, 0.15, 0.17, and 0.32 were obtained respectively (λexc. = 355 nm). These values are significantly higher than those measured for photoinduced arene loss in hydrocarbon solvents using the same excitation wavelength. Laser flash photolysis of (η6-C6H5Y)Cr(CO)3 in 1,1,2-trifluorotrichloroethane

  量子产率从（η芳烃位移6 -C 6 H ^ 5 Y）的Cr（CO）3是在1,1,2-三氟三氯乙烷测量（Y = NH 2，OCH 3，H，CHO，或CO 2 CH 3）。0.24，0.27，分别获得0.15，0.17，和0.32（值λ EXC。  = 355纳米）。这些值明显高于使用相同激发波长在烃类溶剂中光致芳烃损失的测量值。（η的激光闪光光解6 -C 6 H ^ 5 Y）的Cr（CO）3在1,1,2-三氟三氯乙烷（λ EXC。 = 355 nm）导致Cr（CO）6的快速形成（<10 ns）。上（η矩阵隔离实验6 -C 6 H ^ 5 Y）的Cr（CO）3在12 K的CH（Y = H或CHO）4或CO-CH掺杂4点矩阵使用单色的照射证实两个分立的激发态的存在，一种导致CO损失，另一种导致芳烃损失。结果与根据密度泛函理论和时间相关的密度泛函理论计算得出的激发态电子漂移相关。
• The photochemistry of (CO)4Mn(µ-η3:η6-C3H4C6H5)Cr(CO)3 in frozen gas matrices at ca. 12 K
  作者：Paul A. Hamley、Marina K. Kuimova、Alexander J. Blake、Catherine Hughes、Simon B. L. Lyons、Martyn Poliakoff、Anthony H. Wright、Michael W. George

  DOI：10.1039/b206697a

  日期：2003.4.4

  -C3H4C6H5)Cr(CO)3] and [(CO)2(N2)2Mn(μ-η3:η6-C3H4C6H5)Cr(CO)3]. In all these experiments, characterisation of photoproducts was aided by comparison with experiments using the mononuclear fragments [(η6-C6H5C2H5)Cr(CO)3] and [(η3-C3H4C6H5)Mn(CO)4] where we were able to characterise [(η3-C3H4C6H5)Mn(CO)2], [(η6-C6H5C2H5)Cr(CO)2(N2)], [(η3-C3H4C6H5)Mn(CO)3(N2)] and [(η3-C3H4C6H5)Mn(CO)2(N2)2].

  我们已经调查的光化学[（CO）4的Mn（μ-η 3：η 6 -C 3 ħ 4 Ç 6 ħ 5）的Cr（CO）3 ]在低温基质。在氩矩阵，我们看到仅在分子的端部的Mn和CO的损失[（CO）3的Mn（μ-η 3：η 6 -C 3 ħ 4 Ç 6 ħ 5）的Cr（CO）3 ]是唯一的观察到的光产品。然而，在N 2基质中，在两个金属中心都观察到光解，我们能够鉴定[（CO）4 Mn（μ-η3：η 6 -C 3 ħ 4 Ç 6 ħ 5）的Cr（CO） 2（N 2）]，[（CO） 3（N 2）的Mn（μ-η 3：η 6 -C 3 ħ 4 Ç 6 ħ 5）的Cr（CO） 3 ]和[（CO） 2（N 2） 2的Mn（μ-η 3：η 6 -C 3 ħ 4 ç 6 ħ 5）的Cr（CO） 3]。在所有这些实验中，光化的表征通过比较辅助使用所述单核片段[（η实验6 -C 6 H ^ 5 c ^ 2 ^ h 5）的Cr（CO）3
• Photochemistry of (η-benzene)tricarbonylchromium, tricarbonyl-(η-cyclopentadienyl)manganese, and (η-cyclobutadiene)- and (tris-methylenemethane)-tricarbonyliron in frozen gas matrices at 12 K. Infrared spectroscopic evidence for dicarbonylmetal and dicarbonyl-(dinitrogen)metai complexes
  作者：Antony J. Rest、John R. Sodeau、David J. Taylor

  DOI：10.1039/dt9780000651

  日期：——

  Infrared evidence is presented for the formation of co-ordinatively unsaturated species [ML(CO)2][ML = Cr-(η-C6H6), Mn(η-C5H5), or Fe(η-C4H4), or FeC(CH2)H3}] on the u.v. photolysis of [ML(CO)3] complexes in argon and methane matrices, and dinitrogen complexes [ML(CO)2(N2)] in nitrogen matrices at 12 K. The primary photolysis step is readily reversed by visible light for [ML(CO)2] species of Cr and

  红外证据提出了一种用于共ordinatively不饱和物种[ML（CO）的形成2 ] [ML = CR-（η-C 6 H ^ 6），锰（η-C 5 H ^ 5），或Fe（η-C 4 H 4）或Fe C（CH 2）H 3 }]在氩气和甲烷基质中的[ML（CO）3 ]配合物和二氮配合物[ML（CO）2（N 2）]在12 K的氮气中。可见光对Cr和Fe的[ML（CO）2]物种很容易使初级光解步骤逆转，而对于Mn则不容易。关于在溶液相取代反应中作为中间体的配位不饱和物质的假设进行了讨论。
• Photolysis of Group VI metal carbonyls, (η6-C6H6)Cr(CO)3, (η5-C5H5)Mn(CO)3, (η5-CH3C5H4)Mn(CO)3 and (η5-C5H5)Re(CO)3 in Nujol at 77 K
  作者：Thomas E. Bitterwolf、Kimberly A. Lott、Antony J. Rest、Joëlle Mascetti

  DOI：10.1016/0022-328x(91)86168-p

  日期：1991.11

  Photolysis of M(CO)6, where M = Cr,Mo, and W, in Nujol mulls at 77K resulted in the formation of “free” CO and C4v M(CO)5 photoproducts. This reaction was found to be photochemically and thermally reversible. Similarly, the photolysis of the metal “half-sandwich” complexes (η6-C6H6)Cr(CO)3, (η5-C5H5)Mn(CO)3, (η5-CH3C5H4)Mn(CO)3 and (η5-C5H5)Re(CO)3 in Nujol at 77 K was found to form the corresponding

  M（CO）6在Nukol藻中在77K时发生光解，其中M = Cr，Mo和W，导致“游离” CO和C 4 v M（CO）5光产物的形成。发现该反应是光化学和热可逆的。类似地，金属的光解的“半三明治”复合物（η 6 -C 6 H ^ 6）的Cr（CO）3，（η 5 -C 5 H ^ 5）的Mn（CO）3，（η 5 -CH 3 Ç 5 ħ 4）的Mn（CO）3和（η 5 -C 5 H ^ 5发现Nujol中77 K处的Re（CO）3形成相应的二羰基光产物和“游离” CO。发现这些反应是光化学可逆的。（η 6 -C 6 H ^ 6）的Cr（CO）3和（η 5 -C 5）的Re（CO）3，还发现直接在光解，以产生少量的双核的产品，而（η 5 -C 5 H ^ 5）的Mn（CO）3和（η 5 -CH 3 ç 5 ħ 4）的Mn（CO）3形成在退火类似物质。