2,5-bis((trimethylstannyl)ethynyl)thiophene | 207598-63-8

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 2,5-bis((trimethylstannyl)ethynyl)thiophene
• 英文别名: Me3SnC2(μ-1,4-C4H2S)C2SnMe3；trimethyl-[2-[5-(2-trimethylstannylethynyl)thiophen-2-yl]ethynyl]stannane
• CAS: 207598-63-8
• 化学式: C₁₄H₂₀SSn₂
• 分子量: 457.799
• InChiKey: YDPTWBRKTSMHRE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.21
• 重原子数：
  17.0
• 可旋转键数：
  0.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  trans-Fe(depe)₂I₂ 、 2,5-bis((trimethylstannyl)ethynyl)thiophene 以 四氢呋喃 为溶剂， 反应 12.0h， 以88.4%的产率得到
  参考文献：
  名称：

  Structural and Electronic Variations of sp/sp² Carbon-Based Bridges in Di- and Trinuclear Redox-Active Iron Complexes Bearing Fe(diphosphine)₂X (X = I, NCS) Moieties

  摘要：

  Starting from the mononuclear precursor trans-Fe(depe)2I2 (depe = 1,2-bis(diethylphosphino)ethane), four dinuclear complexes IFe(depe)(2)-R-Fe(depe)(2)I, with R = 1,4-(-C C-C6H4-C C-) 1, 1,3-(-C C-C6H4-C C-) 2, 4,4'-(-C C-C6H4-C6H4-C C-) 3, and 2,5-(-C C-thiophene-C C-) 4, as well as a trinuclear complex, {I-Fe(depe)(2)(C C-)}3(1,3,5-C6H3)} 5, were prepared in a facile way by transmetalation from stannylated precursors. Substitution of the terminal iodides applying an excess of NaSCN yielded the corresponding isothiocyanate complexes 6-10 in very good yields. All complexes 1-10 are intrinsically functional due to the redox-active Fe centers embedded in a structurally rigid and covalent sp/sp(2) framework. 1-10 were characterized by NMR, IR, and Raman spectroscopy, as well as elemental analyses. X-ray diffraction studies were carried out for 1, 2, 4, 5, 6, 8, and 9. Cyclic voltammetry was employed to explore the redox behavior of 1-10. The 1,4-(-C C-C6H4-C C-) and the 2,5-(-C C-thiophene-C C-) bridged compounds 1, 4, 6, and 9 exhibit two fully reversible oxidation waves, while the 1,3-(-C C-C6H4-C C-) and 4,4'-(-C C-C6H4-C6H4-C C-) bridged dinuclear complexes and the trinuclear complexes show only one reversible oxidation wave corresponding to 2 e(-) and 3 e(-) processes, respectively. Calculations were carried out for truncated model complexes to determine the HOMO/LUMO energies. The DFT results confirmed that by changing the sp/sp(2) bridging ligand, tuning of the energies of the molecular orbitals and modifying of the HOMO-LUMO gap Delta E(H-L) and the chemical hardness are possible.

  DOI：

  10.1021/om500602m
• 作为产物：
  描述：

  二乙胺基三甲基锡 、 2,5-二(乙炔基)噻吩 生成 2,5-bis((trimethylstannyl)ethynyl)thiophene
  参考文献：
  名称：

  Combined Use of Palladium-Catalyzed Carbon−Carbon and Metal−Carbon Bond Formations for the Construction of Poly(metallaacetylide) Tethers

  摘要：

  The reaction between (eta(5)-C5H4I)Fe(CO)(2)CH3 (2) and 2,5-bis[(trimethylstannyl)ethynyl]thiophene in the presence of palladium affords the iron dimer CH3(CO)(2)Fe(eta(5)-C5H4)C=CC=CHSCH=CC=C(eta(5)-C5H4)Fe(CO)(2)CH3 (4), which upon treatment with I-2 is transformed to the corresponding diiodide I(CO)(2)Fe(eta(5)-C5H4)C=CC=CHSCH=CC=C(eta(5)-C5H4)Fe(CO)(2)I (5). Re action of the latter, in the presence of palladium, with the (trimethylstannyl) acetylide derivatives LnM(eta(5)-C5H4)C=CC=CHSCH=CC=CSn(CH3)(3) (9a, MLn = W(CO)(3)CH3, 9b, MLn = Re(CO)(3)) affords the polymetallaacetylide tethers LnM(eta(5)-C5H4)C=CC=CHSCH=CC=CFe-(CO)(2)(eta(5)-C5H4)C=CC=CHSCH=CC=C(eta(5)-C5H4)(CO)(2)FeC=CC=CHSCH=CC=C(eta(5)-C5H4)-MLn (10, MLn = W(CO)(3)CH3; 11, MLn = Re(CO)(3)). Trimethyltin derivatives of poly(ethynylthiophene) oligomers have been also prepared and tested for their use as spacers in poly(metallaacetylide) complexes.

  DOI：

  10.1021/om971094x

文献信息

• New Access to Homodinuclear Half‐Sandwich Vinylidenemanganese Complexes
  作者：Koushik Venkatesan、Thomas Fox、Helmut W. Schmalle、Heinz Berke

  DOI：10.1002/ejic.200400686

  日期：2005.3

  4-C 4 H 2 S}) and R 2 PCH 2 CH 2 PR 2 (R = Me, Et) at 50 °C for 12 h to yield the corresponding dinuclear complexes in very good yields. These dinuclear tin-substituted vinylidene complexes were further treated with an excess of MeOH to give the corresponding dinuclear parent vinylidene complexes of the type [Mn(MeC 5 H 4 )(R 2 PCH 2 CH 2 PR 2 )=C=C(H)} 2 X}] (X = μ-1,4-C 6 H 4 }, R = Me, 6a; X =

  [Mn(MeC 5 H 4 )(R 2 PCH 2 CH 2 PR 2 )=C=C(SnMe 3 )} 2 X}] ( X = μ-1,4-C 6 H 4 }, R = Me, 2a; X = μ-1,4-C 6 H 4 }, R = Et, 2b; X = μ-1,3 -C 6 H 4 }, R = Me, 3a; X = μ-1,3-C 6 H 4 }, R = Et, 3b; X = μ-4,4-C 6 H 4 -C 6 H 4 }, R = Me, 4a; X = μ-4,4-C 6 H 4 -C 6 H 4 }, R = Et, 4b; X = μ-1,4-C 4 H 2 S }, R = Me, 5a; X = μ-1,4-C 4 H 2 S}, R = Et, 5b) 由[Mn(C 5 H 4 Me) (η 6 -环庚三烯)] 与 0.5 当量。相应的乙炔