tricarbonylbromo(η-cyclopentadienyl)molybdenum

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: tricarbonylbromo(η-cyclopentadienyl)molybdenum
• 英文别名: [(η(5)-Cp)(CO)3MoBr]；[Mo(η-C5H5)(CO)3Br]；(η5-C5H5)(CO)3MoBr；(η5-cyclopentadienyl)Mo(CO)3Br；[MoBr(CO)3(cyclopentadienyl)]；CpMo(CO)3Br
• 化学式: C₈H₅BrMoO₃
• 分子量: 324.97
• InChiKey: TZKHSYVISKXYTG-UHFFFAOYSA-M

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：

  tricarbonylbromo(η-cyclopentadienyl)molybdenum 在 三苯基膦 作用下， 以 苯 为溶剂， 生成 (carbonyl)2(η5-cyclopentadienyl)(PPh3)(Br)molybdenum(II)
  参考文献：
  名称：

  Photochemistry of cyclopentadienylmolybdenum and cyclopentadienyltungsten carbonyl halide complexes

  摘要：

  DOI：

  10.1021/ic50208a022
• 作为产物：
  描述：

  (η5-C5H5)Mo(CO)3H 在 溴甲烷 作用下， 生成 tricarbonylbromo(η-cyclopentadienyl)molybdenum
  参考文献：
  名称：

  Intrinsic barriers to atom transfer: self-exchange reactions of CpM(CO)3X/CpM(CO)3- halide couples

  摘要：

  The self-exchange reactions were followed by H-1 NMR spectroscopy: For the X = 1 complexes, standard line width measurements yield (M = Mo) k(298) = 1.5 x 10(4) M-1 s-1 (DELTA-H = 6.4 (+/- 0.4) kcal mol-1, DELTA-S = -18 (+/- 1.5) cal K-1 mol-1) and (M = W) k(298) = 4.5 x 10(3) M-1 s-1 (DELTA-H = 7.5 (+/- 0.1) kcal mol-1, DELTA-S = -16.8 (+/- 0.5) cal K-1 mol-1). For the X = Br complexes, magnetization-transfer experiments yield (M = Mo) k(298) = 1.6 x 10(1) M-1 s-1 (DELTA-H = 12.1 (+/- 4.5) kcal mol-1, DELTA-S = -12 (+/- 15) cal K-1 mol-1) and (M = W) k(298) = 1.5 M-1 s-1 (DELTA-H = 15.1 (+/- 5.2) kcal mol-1, DELTA-S = -7 (+/- 16) cal K-1 mol-1); H-1 NMR longitudinal relaxation times T1 for the Cp groups of the reactants are typically 40 s. The X = Cl systems were studied by conventional techniques, with the rates of "transfer" of Cp-d5 from (Cp-d5)W(CO)3- to CpW(CO)3Cl being monitored; for M = Mo, k(298) = 9.0 x 10(-2) M-1 s-1 (DELTA-H = 18.9 (+/- 1.0) kcal mol-1, DELTA-S = 0 (+/- 4) cal K-1 mol-1) and for M = W, k(298) = 2.1 x 10(-3) M-1 s-1 (DELTA-H = 17.7 (+/- 3.3) kcal mol-1, DELTA-S = -11 (+/- 11) cal K-1 mol-1). For X = CH3, the CpW(CO)3-/CpW(CO)3CH3 self-exchange rate constant, also determined by monitoring rates of "transfer" of Cp-d5 from (Cpd5)W(CO)3- to CpW(CO)3X, is almost-equal-to 1 x 10(-5) M-1 s-1 at 335 K. The latter self-exchange reaction is discussed in terms of the intrinsic barrier for oxidative addition to the anion. For the X = halogen exchanges, the role of the M(I) ("metal radical") state is considered, and it is concluded that the latter isovalent state is not an intermediate for these systems. However, the isovalent state may serve to stabilize the transition state for two-electron transfer between the metal centers through configuration interaction. Our results, taken with those for other X = halogen systems, indicate that effective transfer of X+ may be intrinsically rapid when both reactants are 18-electron species and steric factors are favorable.

  DOI：

  10.1021/ja00004a024

文献信息

• Organometallic cyclisation reactions. Part II. Formation of molybdenum arsine complexes containing five-membered rings
  作者：Murray Mickiewicz、Kevin P. Wainwright、Stanley Bruce Wild

  DOI：10.1039/dt9760000262

  日期：——

  A reductive cyclisation reaction occurs when complexes of the type [Mo(η-C5H5)(CO)2I(L)](L is a halogen-substituted tertiary arsine) react with sodium amalgam in tetrahydrofuran giving cyclic molybdenum–arsine complexes. The stereochemical non-rigidity of the ring systems in solution has been interpreted in terms of a square-pyramidal–trigonal-bipyramidal isomerisation process. The cyclic complex dicarbonyl

  时，会发生还原环化反应时的类型[沫（η-C的复合物5 ħ 5）（CO）2 I（L）]（L为卤素取代的叔胂）与钠汞齐在四氢呋喃给环状钼-胂反应复合体。环状体系在溶液中的立体化学非刚性已通过正方形-锥体-三角-双锥体的异构化过程进行了解释。环状配合物二羰基（η-环戊二烯基）（3-二甲基ar基丙基-C 1 As）钼（II）容易发生氢化物脱氢反应，形成螯合的烯丙基二甲基ar基的阳离子衍生物。
• Reactivity of 17-electron organometallic tungsten and molybdenum radicals: a laser flash photolysis study
  作者：Susannah L. Scott、James H. Espenson、Zuolin Zhu

  DOI：10.1021/ja00058a025

  日期：1993.3

  constants for reactions with organic halides vary linearly with the concentration of the organic halide; bimolecular rate constants for CpW(CO)[sub 3] range from 3.9 [times] 10[sup 2] L mol[sup [minus]1] s[sup [minus]1] with CH[sub 2]Br[sub 2] to 1.34 [times] 10[sup 9] L mol[sup [minus]1] s[sup [minus]1] for CBr[sub 4]. The reactivity trends (RI > RBr > RCl) and (benzyl > allyl > 3[degrees] > 2[degrees]more »

  [CpW(CO)[sub 3]][sub 2] 或 [CpMo(CO)[sub 3]][sub 2] 的可见 (460--490 nm) 激光闪光光解诱导金属-金属键与形成 17 个电子自由基，CpM(CO)[sub 3]。自由基二聚导致母体二聚体的定量恢复，随后二聚体吸光度的时间分辨增加。反应遵循清晰的二级动力学，-d[CpM(CO)[sub 3]]/dt = 2k[sub c][CpM(CO)[sub 3]][sup 2]；k[sub c](W) = 6.2 [times] 10[sup 9] 和 k[sub c](Mo) = 3.9 [times] 10[sup 9] L mol[sup [minus]1] s[sup [负]1] 在 CH[sub 3]CN 中，温度为 23°C。CpM(CO)[sub 3] 自由基通过原子转移机制与有机和无机卤化物和拟卤化物反应。在大量过量的含卤化
• Formation of tetrakis(trifluoromethyl)cyclobutadiene complexes of molybdenum and the existence of high barriers to rotation of the cyclobutadiene ring
  作者：Jack L. Davidson

  DOI：10.1039/c39800000113

  日期：——

  The syntheses of complexes [Mo(η5-C5H5)η4-C4(CF3)4}(CO)I] and [Mo(η5-C5H5)η4-C4(CF3)4}S2CNMe2] containing a tetrakis(trifluoromethyl)cyclobutadiene ring are described; variable temperature 19F n.m.r. studies reveal the existence of high barriers to rotation of the C4 ring about the metal–ligand axis in both complexes.

  配合物的合成[沫（η 5 -C 5 H ^ 5） η 4 -C 4（CF 3）4 }（CO）I]和[沫（η 5 -C 5 H ^ 5） η 4 -C 4描述了含有四（三氟甲基）环丁二烯环的（CF 3）4 } S 2 CNMe 2 ]；可变温度19 F nmr研究表明，两种配合物中都存在阻碍C 4环绕金属-配体轴旋转的高障碍。
• Alkyne, cyclobutadiene and cyclopentadienone complexes of molybdenum and tungsten
  作者：Jack L. Davidson

  DOI：10.1016/0022-328x(91)86170-u

  日期：1991.11

  Reactions of [MoX(CO)3(η5-C5H5)] (X = Br, I) with CF3CCCF3 in a sealed tube give the tetrakis(trifluoromethyl)cyclopentadienone derivatives [MoX(CO)η4-C4(CF3)4CO}(η5-C5H5)] (3b, c) whereas if the liberated carbon monoxide is removed at intervals the bis-alkyne complexes [MoX(CF3-CCCF3)2(η5-C5H5] (2b, c) are obtained preferentially. With X = 1 the former reaction also gives [MoI(CO)η4-C4(CF3)4}(η5-C5H5)]

  的反应[MOX（CO）3（η 5 -C 5 H ^ 5）（X = Br的，I）与CF 3 CCCF 3在密封的管中得到的四（三氟甲基）环戊二烯酮衍生物[MOX（CO） η 4 -C 4（CF 3）4 CO}（η 5 -C 5 H ^ 5）]（图3b，c ^），而如果释放的一氧化碳被在间隔除去双-炔复合物[MOX（CF 3 -C CCF 3）2（η 5 -C 5 H ^ 5 ]（优选获得2b，c）。其中X = 1的以前的反应也可以得到：MOI（CO）η 4 -C 4（CF 3）4 }（η 5 -C 5 H ^ 5）]（4a中含有η）4四（三氟甲基）环cyclobutadine 。在类似条件下的钨络合物[WX（CO）3（η 5 -C 5 H ^ 5）〕和通式CF 3 CCCF 3只给出双-炔衍生物[WX（CF 3 CCCF 3）2（η 5 -C5 H 5）]（X = Br，I），没
• Cyclopentadienyl Molybdenum(II/VI) N-Heterocyclic Carbene Complexes: Synthesis, Structure, and Reactivity under Oxidative Conditions
  作者：Shenyu Li、Choon Wee Kee、Kuo-Wei Huang、T. S. Andy Hor、Jin Zhao

  DOI：10.1021/om900980a

  日期：2010.4.26

  [CpMo(CO)2(IMes)(CH3CN)][BF4] (6) have been synthesized and fully characterized. The stability of metal−NHC ligand bonds in these compounds under oxidative conditions has been investigated. The thermally stable Mo(VI) dioxo NHC complex [CpMoO2(IMes)][BF4] (9) has been isolated by the oxidation of the ionic complex 6 by TBHP (tert-butyl hydrogen peroxide). Complex 6 can be applied as a very active (TOFs up to 3400

  一系列N杂环卡宾（NHC）配合物CpMo（CO）2（NHC）X（NHC = IMe = 1,3-二甲基咪唑-2-亚烷基，X = Br，1 ; NHC = 1,3-二丙基咪唑-2 -亚烷基，X = Br，2 ; NHC = IMes = 1,3-双（2,4,6-三甲基苯基）咪唑-2-亚烷基，X = Br，3 ; NHC = IBz = 1,3-二苄基咪唑-2 -亚烷基，X = Br，4a，X = Cl，4b ; NHC = 1-甲基-3-丙基咪唑-2-亚烷基，X = Br，5）和[CpMo（CO）2（IMes）（CH 3 CN） ]] [BF 4 ]（6）已被合成并具有充分的特征。研究了这些化合物在氧化条件下金属-NHC配体键的稳定性。通过TBHP（叔丁基过氧化氢）氧化离子络合物6，分离出了热稳定的Mo（VI）二氧羰基NHC络合物[CpMoO 2（IMes）] [BF 4 ]（9）。可以将络

表征谱图