Cp2Mo(η(2)-SC(3-pyridyl)C(H)S) | 178960-92-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: Cp2Mo(η(2)-SC(3-pyridyl)C(H)S)
• 英文别名: cyclopenta-1,3-diene;molybdenum(4+);(Z)-1-pyridin-3-ylethene-1,2-dithiolate
• CAS: 178960-92-4
• 化学式: C₁₇H₁₅MoNS₂
• 分子量: 393.385
• InChiKey: LWGGAJIGNCQISA-PQIWAGTOSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  4.28
• 重原子数：
  21
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  14.9
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Cp2Mo(η(2)-SC(3-pyridyl)C(H)S) 以 N,N-二甲基甲酰胺 为溶剂， 生成 [Mo(C₅H₅)2(SCHC(C₅H₄N)S)]^(1-)
  参考文献：
  名称：

  钼和钨的双（环戊二烯基）二硫辛烯配合物的合成，结构和氧化还原性能†

  摘要：

  化合物[Cp 2 M（S 2 C 2（H）R）]（M = Mo或W； R =苯基，吡啶-2-基，吡啶-3-基，吡啶-4-基或喹喔啉-2- yl）和[Cp 2 Mo（S 2 C 2（Me）（吡啶-2-基）]]的合成方法很简单二硫代烯配合物，即。[Cp 2 MCl 2 ]（M = Mo或W）与二硫代烯通过使相应的4-（R）-1,3-二硫醇-2-酮与CsOH反应生成前体配体。（许这些沫化合物先前报道等，无机化学。 1996，35，4743）; 然而，本文所用的制备方法用途更广，并且以良好的收率产生化合物，并且所有的W化合物都是新的。电化学研究表明，每种化合物都经过扩散控制的单电子氧化（OX I）和单电子还原（RED I） 过程; 与Mo化合物相比，Mo化合物的每次氧化还原变化都具有更高的正电势。通过化学或电化学氧化生成的单阳离子是稳定的，并且[Cp 2 Mo（S 2 C 2（H）R）] + / [Cp

  DOI：

  10.1039/c1dt10663e
• 作为产物：
  描述：

  4-(4'-pyridyl)-1,3-dithiol-2-one 、 二氯二茂钼 在 CsOH*H₂O 作用下， 以 甲醇 为溶剂， 以58%的产率得到Cp2Mo(η(2)-SC(3-pyridyl)C(H)S)
  参考文献：
  名称：

  钼和钨的双（环戊二烯基）二硫辛烯配合物的合成，结构和氧化还原性能†

  摘要：

  化合物[Cp 2 M（S 2 C 2（H）R）]（M = Mo或W； R =苯基，吡啶-2-基，吡啶-3-基，吡啶-4-基或喹喔啉-2- yl）和[Cp 2 Mo（S 2 C 2（Me）（吡啶-2-基）]]的合成方法很简单二硫代烯配合物，即。[Cp 2 MCl 2 ]（M = Mo或W）与二硫代烯通过使相应的4-（R）-1,3-二硫醇-2-酮与CsOH反应生成前体配体。（许这些沫化合物先前报道等，无机化学。 1996，35，4743）; 然而，本文所用的制备方法用途更广，并且以良好的收率产生化合物，并且所有的W化合物都是新的。电化学研究表明，每种化合物都经过扩散控制的单电子氧化（OX I）和单电子还原（RED I） 过程; 与Mo化合物相比，Mo化合物的每次氧化还原变化都具有更高的正电势。通过化学或电化学氧化生成的单阳离子是稳定的，并且[Cp 2 Mo（S 2 C 2（H）R）] + / [Cp

  DOI：

  10.1039/c1dt10663e

文献信息

• Metallo 2,3-Disulfidothienoquinoxaline, 2,3-Disulfidothienopyridine, and 2-Sulfido-3-oxidothienoquinoxaline Complexes:  Synthesis and Characterization
  作者：Sharada P. Kaiwar、John K. Hsu、Anthony Vodacek、Glenn Yap、Louise M. Liable-Sands、Arnold L. Rheingold、Robert S. Pilato

  DOI：10.1021/ic961428v

  日期：1997.5.1

  The 2,3-disulfidothienoquinoxaline complexes of Cp2Mo and dppePd and the 2,3-disulfidothienopyridine complexes of Cp2Mo were obtained as products from the S-8 oxidation of the corresponding metallo-1,2-enedithiolate complexes. The analogous 2-sulfido-3-oxidothienoquinoxaline complexes of Cp2Ti, Cp2Mo, dppPd, and dppePt were prepared from 1-(quinoxalin-2-yl)-2-bromoethanone and the corresponding polysulfido complex. Both Cp2MoS2C10H4N2S} and Cp2MoSOC10H4N2S} have been characterized crystallographically. These complexes contain an extended planar ring where the metal is bound to substituents at the 2- and 3-positions of the thiophene ring. The oxidation products of the Cp2Mo derivatives all have EPR g values near 1.98 and Mo-97/95 hyperfine of less than or equal to 8.5 G. All of the complexes have a visible band assigned to an intraligand transition (IL). The excitation of a room-temperature DMSO solution of dppePtSOC10H4N2S} leads to an emission at 690 nm with a phi = 0.005. Lifetime measurements were best fit as the sum of two exponential decays with lifetimes of 6 and 0.3 ns.
• Direct Conversion of α-Substituted Ketones to Metallo-1,2-enedithiolates
  作者：John K. Hsu、Cecilia J. Bonangelino、Sharada P. Kaiwar、Christine M. Boggs、James C. Fettinger、Robert S. Pilato

  DOI：10.1021/ic9602052

  日期：1996.1.1

  A new synthetic route to metallo-1,2-enedithiolates is presented. The addition of 1 equiv of the a-bromo ketones Ar-C(O)CHXR (X = Pr) Ar = 2-quinoxaline, 2-, 3-, or 4-pyridine, Ph, CI-Ph, and pyrene (R = H); Ar = 2-quinoxaline (R = Me); and Ar = R = Ph} to Cp(2)Mo(SH)(2) followed by the addition of base results in the formation of the corresponding metallo-l,2-enedithiolate Cp(2)Momu(2)-SC(Ar)C(R)S}. The alpha-tosyl ketones quinoxaline -C(O)CHR-tosyl R = H, Me} and the alpha-phosphorylated ketone 3-pyridine-C(O)CH2-O-P(O)(OEt)(2) yield the same products as the corresponding alpha-bromo ketones upon reaction with Cp(2)Mo(SH)(2). The addition of acid to the heterocyclic substituted complexes yields Cp(2)Moeta(2)-SC(HetH(+))C(R)S}. Both Cp(2)Moeta(2)-SC(quinoxaline)C(H)S} and [Cp(2)Moeta(2)-SC(quinoxalinium)C(H)S}][BF4] have been crystallographically characterized. Cp(2)Moeta(2)-SC(quinoxaline)C(H)S} crystalizes in the C2/c space group with a = 21.451(2) Angstrom, b = 15.474 Angstrom, c = 12.2201(13) Angstrom, and beta = 107.440(7)degrees. [Cp(2)Mo space group with a = 7.4009(8) Angstrom, b = 10.1192(13)degrees Angstrom, c 15.930(4) Angstrom; alpha = 81.49(2)degrees, beta = 76.14(2)degrees, and gamma = 85.784 degrees. In the solid state [Cp(2)Moeta(2)-SC(quinoxalinium)C(H)S}][BF4] pi-stacks the heterocycle of two adjacent molecules with atom-atom distances of approximate to 3.6 Angstrom. The stacks are limited to pairs of molecules, and there is no long-range order. The pK(a) values for the quinoxalinium (R = H and Me) and the 2-, 3-, and 4-pyridinium (R = H) complexes have been determined in acetonitrile to be 1-3 units larger than the free heterocycles. The pK(a) of the pyridinium complexes follows the substitution trend 2 approximate to 4 > 3 > free pyridinium and is consistent with resonance stabilization of pyridinium by the metallo-l,2-enedithiolate. Electronic transitions in these complexes have been assigned to a LMCT transition and an ILCT transition by comparison of the various complexes accompanied with solvent sensitivity studies.