3,4-dimethyl-1,1-diphenyl-1-stannylcyclopent-3-ene | 1147101-06-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3,4-dimethyl-1,1-diphenyl-1-stannylcyclopent-3-ene
• 英文别名: 3,4-dimethyl-1,1-diphenyl-1-stannacyclopent-3-ene；3,4-dimethyl-1,1-diphenylstannacyclopent-3-ene
• CAS: 1147101-06-1
• 化学式: C₁₈H₂₀Sn
• 分子量: 355.067
• InChiKey: SIVCROOLKUSCPS-MBNGEVHQSA-N

物化性质

• 沸点：
  378.8±45.0 °C(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  19.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  3,4-dimethyl-1,1-diphenyl-1-stannylcyclopent-3-ene 在 萘 、 lithium 、 magnesium 、 1,2-二溴乙烷 作用下， 以 四氢呋喃 、 全氘代环己烷 为溶剂， 反应 8.0h， 生成 (2,3-二甲基-2-丁烯-1,4-二基)镁
  参考文献：
  名称：

  溶液中锡烷环戊-3-烯的光解直接检测，二聚化和化学捕集二甲基锡和二苯基锡

  摘要：

  Dimethyl- and diphenylstannylene (SnMe2 and SnPh2, respectively) have been successfully detected and characterized in solution. The stannylenes were generated by photolysis of 1,1,3trimethy1-4-phenyl- (2) and 3,4-dimethy1-1,1-diphenylstannacydopent-3-ene (3), respectively, which have been shown to extrude the species cleanly and in high (0.6 < Phi <0.8) quantum yields through trapping studies using dichlorodimethylstannane (Me2SnCl2) as the stannylene substrate. Laser flash photolysis of 2 and 3 in deoxygenated hexanes affords promptly formed transient absorptions assigned to SnMe2 (lambda(max) = 500 nm; epsilon(500) = 1800 +/- 600 M-1 cm(-1)) and SnPh2 (lambda(max) = 290, 505 nm; 8500 = 2500 +/- 600 M-1 cm(-1)), respectively, which decay with absolute second-order rate constants within a factor of 2 of the diffusional limit in both cases. The decay of the stannylenes is accompanied by the growth of new transient absorptions ascribable to the corresponding dimers, the structures of which are assigned with the aid of DFT and time-dependent (TD) DFT calculations at the (TD)omega B97XD/6-31+G(d,p)(C,H,O)-LANL2DZdp(sn) level of theory. Dimerization of SnMe2 affords a species exhibiting lambda(max) = 465 nm, which is assigned to the expected Sn=Sn doubly bonded dimer, tetramethyldistannene (Me2Sn=SnMe2, 16a), in agreement with earlier work. In contrast, the spectrum of the dimer formed from SnPh2 exhibits strong absorptions in the 280-380 nm range and a very weak absorption at 650 nm, on the basis of which it is assigned to phenyl(triphenylstanny)stannylene (17b). The calculations suggest that 17b is formed via ultrafast rearrangement of a novel phenyl-bridged stannylidenestannylene intermediate (20), which can be formed either directly by "endo" dimerization of SnPh2 or by isomerization of the "exo" dimer, tetraphenyldistannene (16b); the predicted barriers for these rearrangements are consistent with the experimental finding that the observed product is formed at close to the diffusion-controlled rate. Absolute rate and equilibrium constants are reported for the reactions of SnMe2 and SnPh2 with Me2SnCl2 and methanol (MeOH), respectively, in hexanes at 25 degrees C.

  DOI：

  10.1021/acs.organomet.5b00615
• 作为产物：
  描述：

  2,3-二甲基-1,3-丁二烯 在 萘 、 lithium 、 magnesium 、 1,2-二溴乙烷 作用下， 以 四氢呋喃 为溶剂， 反应 16.0h， 生成 3,4-dimethyl-1,1-diphenyl-1-stannylcyclopent-3-ene
  参考文献：
  名称：

  溶液中锡烷环戊-3-烯的光解直接检测，二聚化和化学捕集二甲基锡和二苯基锡

  摘要：

  Dimethyl- and diphenylstannylene (SnMe2 and SnPh2, respectively) have been successfully detected and characterized in solution. The stannylenes were generated by photolysis of 1,1,3trimethy1-4-phenyl- (2) and 3,4-dimethy1-1,1-diphenylstannacydopent-3-ene (3), respectively, which have been shown to extrude the species cleanly and in high (0.6 < Phi <0.8) quantum yields through trapping studies using dichlorodimethylstannane (Me2SnCl2) as the stannylene substrate. Laser flash photolysis of 2 and 3 in deoxygenated hexanes affords promptly formed transient absorptions assigned to SnMe2 (lambda(max) = 500 nm; epsilon(500) = 1800 +/- 600 M-1 cm(-1)) and SnPh2 (lambda(max) = 290, 505 nm; 8500 = 2500 +/- 600 M-1 cm(-1)), respectively, which decay with absolute second-order rate constants within a factor of 2 of the diffusional limit in both cases. The decay of the stannylenes is accompanied by the growth of new transient absorptions ascribable to the corresponding dimers, the structures of which are assigned with the aid of DFT and time-dependent (TD) DFT calculations at the (TD)omega B97XD/6-31+G(d,p)(C,H,O)-LANL2DZdp(sn) level of theory. Dimerization of SnMe2 affords a species exhibiting lambda(max) = 465 nm, which is assigned to the expected Sn=Sn doubly bonded dimer, tetramethyldistannene (Me2Sn=SnMe2, 16a), in agreement with earlier work. In contrast, the spectrum of the dimer formed from SnPh2 exhibits strong absorptions in the 280-380 nm range and a very weak absorption at 650 nm, on the basis of which it is assigned to phenyl(triphenylstanny)stannylene (17b). The calculations suggest that 17b is formed via ultrafast rearrangement of a novel phenyl-bridged stannylidenestannylene intermediate (20), which can be formed either directly by "endo" dimerization of SnPh2 or by isomerization of the "exo" dimer, tetraphenyldistannene (16b); the predicted barriers for these rearrangements are consistent with the experimental finding that the observed product is formed at close to the diffusion-controlled rate. Absolute rate and equilibrium constants are reported for the reactions of SnMe2 and SnPh2 with Me2SnCl2 and methanol (MeOH), respectively, in hexanes at 25 degrees C.

  DOI：

  10.1021/acs.organomet.5b00615

文献信息

• Fast kinetics studies of the Lewis acid–base complexation of transient stannylenes with σ- and π-donors in solution
  作者：Ian R. Duffy、William J. Leigh

  DOI：10.1039/c8cp03580f

  日期：——

  310–405 nm depending on the donor and substitution at tin. Bimolecular rate constants for complexation (kC), which could be determined for 14 of the 24 Lewis pairs that were studied, were found to fall within a factor of four of the diffusional limit in all cases, with SnMe2 showing consistently higher reactivity than SnPh2. Equilibrium constants for complexation (KC) could be measured for all but one

  通过激光光解方法研究了二甲基和二苯基锡（分别为SnMe 2和SnPh 2）在己烷溶液中的路易斯酸碱络合化学。两种亚锡与一系列九个O-，S-和N-供体（包括环状和无环二烷基醚和硫化物，伯，仲和叔胺，乙酸乙酯和丙酮），两个烯烃和一个炔烃迅速而可逆地产生相应的亚锡-供体路易斯对，在每种情况下均已通过时间分辨紫外可见吸收光谱法对其进行了检测。配合物表现出的范围内的UV-vis吸收最大值λ最大约310-405 nm，取决于施主和锡上的取代。对于所有研究的24个Lewis对中的14个，可以确定的络合物的双分子速率常数（k C）在所有情况下都位于扩散极限的四分之一之内，其中SnMe 2的反应活性始终高于SnPh 2。用于络合（平衡常数ķ Ç）可以为所有，但stannylene-π-和O-供体对一个待测量中，对应于（气相）在结合的1.1的范围内自由能，以-3.9千卡摩尔的值- 1。SnMe 2和SnPh
• Synthesis of 1-Stannacyclopent-3-enes and Their Pyrolysis to Stannylenes
  作者：Dong Zhou、Clemens Reiche、Mrinmoy Nag、John A. Soderquist、Peter P. Gaspar

  DOI：10.1021/om800541f

  日期：2009.4.27

  1,1-Diorgano-1-stannacyclopent-3-enes have been synthesized by condensation in THF of magnesium complexes of 1,3-dienes and dichlorodiorganostannanes. 1, 1-Dimethyl-, 1, 1-di-n-butyl-,1, 1-di-tert-butyl-, and 1,1-diphenyl-1-stannacyclopent-3-enes and 1,1,3,4-tetramethyl-, 1,1-di-tert-butyl-3,4-dimethyl-, and 3,4-dimethyl-1,1-diphenyl-1-stannacyclopent-3-enes were prepared. Kinetic studies of the pyrolysis. at temperatures as low as 75 degrees C of several of these stannacyclopent-3-enes resulted in their first-order disappearance, consistent with a unimolecular dissociation to the corresponding stannylene and diene. Activation parameters are reported. Trapping of dimethylstannylene by dienes was overwhelmed by oligomerization of Me2Sn::, but for t-Bu2Sn: a high yield of diene adduct was obtained. The dimethylstannylene oligomer(s) functioned as stannylenoids and were responsible for several reactions previously attributed to free Me2Sn:. cyclo-(t-Bu2Sn)(4) may also function as a stannylenoid.