(η5-cyclopentadienyl)W(CO)3Br

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: (η5-cyclopentadienyl)W(CO)3Br
• 英文别名: (η(5)-C5H5)WBr(CO)3；[(η(5)-Cp)(CO)3WBr]；[WBr(η-C5H5)(CO)3]
• 化学式: C₈H₅BrO₃W
• 分子量: 412.88
• InChiKey: BDXMCOFXRHZHGY-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：

  (η5-cyclopentadienyl)W(CO)3Br 在 三苯基膦 作用下， 以 苯 为溶剂， 生成 cis-(η5-C5H5)W(CO)2(PPh3)Br
  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：

  carbon monoxide,cyclopenta-1,3-diene,tungsten 在 溴甲烷 作用下， 生成 (η5-cyclopentadienyl)W(CO)3Br
  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

• Alcohol Complexes of Tungsten Prepared by Ionic Hydrogenations of Ketones
  作者：Jeong-Sup Song、David J. Szalda、R. Morris Bullock

  DOI：10.1021/om010222l

  日期：2001.7.1

  gives related [Cp(CO)3W(alcohol)]+OTf- complexes. Aldehydes are selectively hydrogenated over ketones, and alkyl ketones are selectively hydrogenated over aromatic ketones. Hydrogenation of acetophenone gives ethylbenzene, with no intermediate tungsten complexes being observed. Reaction of 1-phenyl-1,3-butanedione with Cp(CO)3WH and HOTf gave Cp(CO)3W[CH3CH(OH)CH2C(O)Ph]}+OTf -, the structure of which

  由CP（CO）的丙酮氢化离子3 WH和HOTf（OTF = OSO 2 CF 3），得到2-丙醇复杂的[Cp（CO）3 W（HO我PR）] +光学传递函数- 。1 H NMR数据表明，醇OH与溶液中的三氟甲磺酸根阴离子的氧之间存在OH-·O氢键，该配合物的晶体结构表明氢键也以固态存在。短的O···O距离为2.63（1）Å表示氢键很强。其它酮和醛的加氢给出了相关的[Cp（CO）3 W（醇）] +光学传递函数-复合体。醛在酮上选择性地氢化，烷基酮在芳族酮上选择性地氢化。苯乙酮加氢生成乙苯，未观察到任何中间体钨配合物。1-苯基-1,3-丁二酮与CP（CO）的反应3 WH和HOTf，得到CP（CO）3 W [CH 3 CH（OH）CH 2 C（O）PH]} +光学传递函数- ，结构其通过X射线衍射测定。的醇配合物的[Cp（CO）3 W（醇）] +光学传递函数-分解溶液中，得到游离醇类和CP（CO）3
• 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
• 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
• Reactions of carbonylmetallate anions with 1-haloalkynes
  作者：N. A. Ustynyuk、T. V. Filatova、V. N. Vinogradova、L. I. Leont'eva、O. V. Semeikin、L. M. Epshtein、E. S. Shubina、L. N. Saitkulova、E. V. Bakhmutova、A. L. Chistyakov、I. V. Stankevich

  DOI：10.1007/bf02496023

  日期：1999.6

  [(η5-C5R′5)(CO)3M]− (R′ = H (1–3),, M=Cr (1), M=Mo (2), or M=W (3); R′ =Me (4–6), M=Cr (4), M=Mo (5), or M=W (6) were revealed. It was established that the first stage of the reactions of anions1–6 with bromo- or iodoalkynes RC≡CX (X=Br or I) involved the transfer of the halogen atom from the sp-hybridized carbon atom to the transition metal atom to form carbonyl halides [(η5-C5R′5)(CO)3MX. To the

  这些反应路径与通过MNDO/PM3方法计算的PhC≡CX分子（X=Cl、Br或I）中最低未占分子轨道（LUMO）的结构一致。在 1-氯庚炔-1 C1C≡CC5H11n 的反应中，阴离子 1-3 似乎亲核性不足，但这些反应可以通过钯配合物催化的羰基金属阴离子与氯炔的交叉偶联来进行。
• Beletskaya, I. P.; Suleimanov, G. Z.; Mekhdiev, R. Yu., Doklady Chemistry, 1986, vol. 286 - 291, p. 237 - 239
  作者：Beletskaya, I. P.、Suleimanov, G. Z.、Mekhdiev, R. Yu.、Khandozhko, V. N.、Petrovskii, P. V.、Kolobova, N. E.

  DOI：——

  日期：——