4,4,8,8-tetramethyl-8-sila-4-stannatetrahydro-s-indacene | 134767-16-1

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机过渡后金属化合物
• 英文名称: 4,4,8,8-tetramethyl-8-sila-4-stannatetrahydro-s-indacene
• 英文别名: 2,2,8,8-Tetramethyl-2-sila-8-stannatricyclo[7.3.0.03,7]dodeca-1(12),3,5,10-tetraene
• CAS: 134767-16-1
• 化学式: C₁₄H₂₀SiSn
• 分子量: 335.108
• InChiKey: UKOYXMFLJOATIA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.23
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (η5-cyclopentadienyl)trichlorozirconium bis(tetrahydrofuran) 、 4,4,8,8-tetramethyl-8-sila-4-stannatetrahydro-s-indacene 以 甲苯 为溶剂， 以72%的产率得到
  参考文献：
  名称：

  Synthesis of bimetallic complexes via 4-stannatetrahydro-s-indacenes

  摘要：

  4-Stanna-8-silatetrahydro-4,4,8,8-tetramethyl-s-indacene (4) reacts with CpTiCI3 and CpZrCl3.2THF in toluene (ratio 1:1) to give monotransmetallated products CPMC12 (eta5-C5H4SiMe2C5H4SnMe2CI) (M = Ti (5), Zr (6)) in high yields. These compounds can be transformed into heteronuclear complexes of type L(n)MCp-SiMe2-CpM'L'm (ML, = TiCl2CP, M'L'm = Rh(COD), 10; ML(n) = ZrCl2CP, M'L'm = Rh(COD), 11; ML(n) = ZrCl2CP, M'L'm = TiCl2CP, 12; ML(n) = ZrCl2CP, M'L'm = ZrCl2CP*, 13) in reactions with [Rh(COD)Cl]2, CpTiCI3, and Cp*ZrCl3, respectively. Compound 4 and its heteroanalog 4-stannatetra-hydro-4,4,8,8-tetramethyl-s-indacene (14) react with CpTiCI3 (ratio 1:2) and (Cl3TiCP)2SiMe2 (16) (ratio 1:1) to give the corresponding monobridged [CpTiCl2(eta5-C5H4)]2XMe2 (X = C (15), Si (8)) and doubly-bridged (eta5:eta5-C5H4SiMe2C5H4) (eta5:eta5-C5H4XMe2C5H4)(TiCl2)2 (X = C (17), Si (18)) Ti(IV) derivatives. They may be reduced by powdered zinc in toluene to the corresponding Ti(III) complexes, [CpTiCl(eta5-C5H4)]2XMe2 (X = C (20), Si (21)) and (eta5:eta5-C5H4SiMe2C5H4) (eta5:eta5-C5H4XMe2C5H4)(TiCl)2 (X = C (22), Si (23)). Crystals of 23 are monoclinic, space group P2(1)/a with unit cell dimensions a = 16.033 (3) angstrom, b = 18.859 (4) angstrom, c = 7.997 (2) angstrom, gamma = 96.82 (2)-degrees, and Z = 4.

  DOI：

  10.1021/om00060a007
• 作为产物：
  描述：

  bis-(cyclopentadienyl)dimethylsilane 、 二甲基二氯化锡 在 BuLi 作用下， 以 乙醚 、 正己烷 为溶剂， 以54%的产率得到4,4,8,8-tetramethyl-8-sila-4-stannatetrahydro-s-indacene
  参考文献：
  名称：

  Synthesis of bimetallic complexes via 4-stannatetrahydro-s-indacenes

  摘要：

  4-Stanna-8-silatetrahydro-4,4,8,8-tetramethyl-s-indacene (4) reacts with CpTiCI3 and CpZrCl3.2THF in toluene (ratio 1:1) to give monotransmetallated products CPMC12 (eta5-C5H4SiMe2C5H4SnMe2CI) (M = Ti (5), Zr (6)) in high yields. These compounds can be transformed into heteronuclear complexes of type L(n)MCp-SiMe2-CpM'L'm (ML, = TiCl2CP, M'L'm = Rh(COD), 10; ML(n) = ZrCl2CP, M'L'm = Rh(COD), 11; ML(n) = ZrCl2CP, M'L'm = TiCl2CP, 12; ML(n) = ZrCl2CP, M'L'm = ZrCl2CP*, 13) in reactions with [Rh(COD)Cl]2, CpTiCI3, and Cp*ZrCl3, respectively. Compound 4 and its heteroanalog 4-stannatetra-hydro-4,4,8,8-tetramethyl-s-indacene (14) react with CpTiCI3 (ratio 1:2) and (Cl3TiCP)2SiMe2 (16) (ratio 1:1) to give the corresponding monobridged [CpTiCl2(eta5-C5H4)]2XMe2 (X = C (15), Si (8)) and doubly-bridged (eta5:eta5-C5H4SiMe2C5H4) (eta5:eta5-C5H4XMe2C5H4)(TiCl2)2 (X = C (17), Si (18)) Ti(IV) derivatives. They may be reduced by powdered zinc in toluene to the corresponding Ti(III) complexes, [CpTiCl(eta5-C5H4)]2XMe2 (X = C (20), Si (21)) and (eta5:eta5-C5H4SiMe2C5H4) (eta5:eta5-C5H4XMe2C5H4)(TiCl)2 (X = C (22), Si (23)). Crystals of 23 are monoclinic, space group P2(1)/a with unit cell dimensions a = 16.033 (3) angstrom, b = 18.859 (4) angstrom, c = 7.997 (2) angstrom, gamma = 96.82 (2)-degrees, and Z = 4.

  DOI：

  10.1021/om00060a007

文献信息

• Reactions of SnMe₂-Bridged Bis(cyclopentadienes) with Iron Pentacarbonyl: Migration of the SnMe₂ Group
  作者：Bolin Zhu、Yuan Li、Yunfei Chen、Wei Shi

  DOI：10.1021/om201151c

  日期：2012.4.23

  In reactions of the singly bridged bis(cyclopentadiene) (SnMe2)((BuC5H4)-Bu-i)(2) (1) or the doubly bridged bis(cyclopentadienes) (SiMe2)(SnMe2)(RC5H3)(2) (R = H (2), R = Bu-t (3)) with Fe(CO)(5) in refluxing xylene, the bridging SnMe2 group migrates from the ligand to the iron atoms to give compounds (5, 7, 9a,b) containing the Fe-Sn-Fe units, together with the corresponding destannylated products (6, 8, 10a,b); the bridging SiMe2 group (in 2 and 3) does not migrate. However, in the reaction of the doubly bridged ligand (GeMe2)(SnMe2)(C5H4)(2) (4) with Fe(CO)(5), the SnMe2 group undergoes a similar migration to produce the complex GeMe2[(eta(5)-C5H4)Fe(CO)(2)](2)SnMe2 (12), containing the Fe-Sn-Fe unit, both SnMe2 and GeMe2 groups migrate from the ligand to the iron atoms to yield the product [(GeMe2)(eta(5)-C5H4)Fe(CO)(2)][(SnMe2)(eta(5)-C5H4)Fe(CO)(2)] (11), containing one Fe-Ge bond and one Fe-Sn bond, or the SnMe2 group is cleaved to afford the destannylation product GeMe2[(eta(5)-C5H4)Fe(CO)](2)(mu-CO)(2) (13). The stability of complexes 5, 7, and 12 containing the Fe-Sn-Fe unit toward heat and light was also studied. The molecular structures of 9a,b, 11, and 12 were determined by X-ray diffraction.
• Reactions of SnMe2-bridged biscyclopentadienes with molybdenum carbonyl to give compounds containing Mo–Sn–Mo units
  作者：Bo-Lin Zhu、Yuan Li、Yun-Fei Chen、Wei Shi

  DOI：10.1016/j.poly.2012.03.011

  日期：2012.5

  In the reactions of double-bridged biscyclopentadienes (EMe2)(SnMe2)(RC5H3)(2) (E = C (1), E = Si (2 or 4), E = Ge (3)), or single-bridged biscyclopentadiene (SnMe2)((BuC5H4)-Bu-t)(2) (5) with Mo(CO)(6) in refluxing xylene, the bridging SnMe2 group migrates from the ligand to the molybdenum atoms to give compounds (6-10) containing the Mo-Sn-Mo units; the bridging group EMe2 (E = C or Si in 1, 2, or 4) does not migrate. It is noteworthy that [(eta(5)-C5H5)Mo(CO)(3)](2)SnMe2 (8) obtained from the reaction of (GeMe2)(SnMe2)(C5H4)(2) (3) with Mo(CO)(6) is a degermylated and SnMe2 group migrated product, another outcome worth mentioning is that the complex 9 is afforded only in the rac-configuration. The stability of complexes (6, 7, and 10) containing the Mo-Sn-Mo unit toward heat and light was also studied. The molecular structures of 6, 9, and 10 were determined by X-ray diffraction. (C) 2012 Elsevier Ltd. All rights reserved.
• Synthesis of bimetallic complexes via 4-stannatetrahydro-s-indacenes
  作者：I. E. Nifant'ev、M. V. Borzov、A. V. Churakov、Sh. G. Mkoyan、L. O. Atovmyan

  DOI：10.1021/om00060a007

  日期：1992.12

  4-Stanna-8-silatetrahydro-4,4,8,8-tetramethyl-s-indacene (4) reacts with CpTiCI3 and CpZrCl3.2THF in toluene (ratio 1:1) to give monotransmetallated products CPMC12 (eta5-C5H4SiMe2C5H4SnMe2CI) (M = Ti (5), Zr (6)) in high yields. These compounds can be transformed into heteronuclear complexes of type L(n)MCp-SiMe2-CpM'L'm (ML, = TiCl2CP, M'L'm = Rh(COD), 10; ML(n) = ZrCl2CP, M'L'm = Rh(COD), 11; ML(n) = ZrCl2CP, M'L'm = TiCl2CP, 12; ML(n) = ZrCl2CP, M'L'm = ZrCl2CP*, 13) in reactions with [Rh(COD)Cl]2, CpTiCI3, and Cp*ZrCl3, respectively. Compound 4 and its heteroanalog 4-stannatetra-hydro-4,4,8,8-tetramethyl-s-indacene (14) react with CpTiCI3 (ratio 1:2) and (Cl3TiCP)2SiMe2 (16) (ratio 1:1) to give the corresponding monobridged [CpTiCl2(eta5-C5H4)]2XMe2 (X = C (15), Si (8)) and doubly-bridged (eta5:eta5-C5H4SiMe2C5H4) (eta5:eta5-C5H4XMe2C5H4)(TiCl2)2 (X = C (17), Si (18)) Ti(IV) derivatives. They may be reduced by powdered zinc in toluene to the corresponding Ti(III) complexes, [CpTiCl(eta5-C5H4)]2XMe2 (X = C (20), Si (21)) and (eta5:eta5-C5H4SiMe2C5H4) (eta5:eta5-C5H4XMe2C5H4)(TiCl)2 (X = C (22), Si (23)). Crystals of 23 are monoclinic, space group P2(1)/a with unit cell dimensions a = 16.033 (3) angstrom, b = 18.859 (4) angstrom, c = 7.997 (2) angstrom, gamma = 96.82 (2)-degrees, and Z = 4.