(3,3-dimethylbut-1-yn-1-yl)diphenylsilane | 855313-96-1

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (3,3-dimethylbut-1-yn-1-yl)diphenylsilane
• 英文别名: 3,3-Dimethylbut-1-ynyl(diphenyl)silane；3,3-dimethylbut-1-ynyl(diphenyl)silane
• CAS: 855313-96-1
• 化学式: C₁₈H₂₀Si
• 分子量: 264.442
• InChiKey: CUMRMXAWJIVOEO-UHFFFAOYSA-N

物化性质

• 沸点：
  343.2±25.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.62
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 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：

  (3,3-dimethylbut-1-yn-1-yl)diphenylsilane 、 [(η⁵-C₅Me₅)(CO)₂W(NCMe)Me] 以 not given 为溶剂， 以63%的产率得到[(η5-C5Me5)(CO)2W(SiPh2)(CCtBu)]
  参考文献：
  名称：

  η:η-Alkynyl-Bridged W−Si Complexes:  Formation, Structure, and Reaction with Acetone

  摘要：

  Reactions of (eta5-C5Me4R)(CO)2(MeCN)WMe (R = Me, Et) with HPh2SiCCtBu gave the novel alkynyl-bridged W-Si complexes, (eta5-C5Me4R)(CO)2W(mu-eta1:eta2-CCtBu)(SiPh2) (R = Me, Et), whose alkynyl ligands bridge the tungsten and silicon atoms in an eta1:eta2-coordination mode. The structures of these complexes were fully characterized, including X-ray crystallography. Treatment of (eta5-C5Me5)(CO)2W(mu-eta1:eta2-CCtBu)(SiPh2) with acetone resulted in acetone insertion into the silicon-alkynyl linkage followed by intramolecular C-H activation of the tBu group to give the chelate-type alkyl-alkene complex, (eta5-C5Me5)(CO)2W(eta1:eta2-CH2CMe2C=CHSiPh2OCMe2).

  DOI：

  10.1021/ja050441o
• 作为产物：
  描述：

  3,3-二甲基-1-丁炔 、 氯化二苯基硅烷 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 0.5h， 以86%的产率得到(3,3-dimethylbut-1-yn-1-yl)diphenylsilane
  参考文献：
  名称：

  Al和Ga官能化的硅烷和锗烷的CO2和CS2的氢化硅烷化和氢化锗化–形成甲硅烷基和二甲硅烷基缩醛的协同反应性

  摘要：

  所述alkynylelement氢化物的Hydrometallation我镨2 E（2H）-C≡C-吨卜（1 ; E =硅，锗），其中R 2 M-H [M =铝，镓; R =吨卜，CH（森达3）2 ]在中等产率的Al和Ga官能alkenylsilanes和得到-germanes我镨2 E（H）C（MR 2）= CH-吨BU（2）。空气和湿气敏感的Al化合物在温和的条件下（室温，1 bar）与CO 2反应生成甲酸酯[ i Pr 2 EC（AlR 2）= C（H）– t通过C = O插入E–H键和第二个O原子与铝的配位来生成Bu] O 2 CH（3）。乙缩醛MeAl [C（Si i Pr 2）= CH- t Bu] 2 O 2 CH 2（4a）作为独特的副产物获得。路易斯酸较少的酸性Ga化合物2c即使在较高的温度和压力下也不会与CO 2反应。与CS 2反应生成二硫缩醛[ i Pr 2 EC（M

  DOI：

  10.1002/ejic.202000723

文献信息

• Sodium triethylborohydride as a catalyst for the dehydrogenative silylation of terminal alkynes with hydrosilanes
  作者：Maciej Skrodzki、Samanta Witomska、Piotr Pawluć

  DOI：10.1039/c8dt00684a

  日期：——

  sodium triethylborohydride-catalyzed C(sp)–H bond silylation is reported. The reaction of aromatic and aliphatic alkynes with aromatic hydrosilanes and hydrosiloxanes proceeded in a highly selective manner to afford dehydrocoupling products. Competitive hydrosilylation of the terminal alkyne did not occur as a side-reaction. In view of the above it is remarkable that NaHBEt3 is commonly used as a reducing

  报道了三乙基硼氢化钠催化的C（sp）–H键甲硅烷基化的第一个例子。芳族和脂族炔烃与芳族氢硅烷和氢硅氧烷的反应以高度选择性的方式进行，得到脱氢偶联产物。末端炔烃的竞争性氢化硅烷化未发生为副反应。鉴于上述情况，值得注意的是，NaHBEt 3通常用作在其他氢化硅烷化反应中原位产生活性过渡金属催化剂的还原剂。
• η³-Silapropargyl/Alkynylsilyl Molybdenum Complexes: Synthesis, Structure, and Reactivity toward Methanol
  作者：Mako Yabe-Yoshida、Chizuko Kabuto、Kuninobu Kabuto、Eunsang Kwon、Hiroyuki Sakaba

  DOI：10.1021/ja9005833

  日期：2009.7.8

  Novel eta(3)-silapropargyl/alkynylsilyl complexes Cp*(CO)(2)Mo(eta(3)-Ph(2)SiCCR) (3a, R = (t)Bu; 3b, R = (i)Pr) were synthesized by the reactions of Cp*(CO)(2)(MeCN)MoMe (1) with alkynylsilanes HPh(2)SiC[triple bond]CR. The structures of 3a and 3b were fully characterized by NMR spectroscopy and X-ray crystallography. The reaction of 3a with MeOH at room temperature gave the stable four-membered metallacycle

  新型eta(3)-硅炔基/炔基甲硅烷基配合物Cp*(CO)(2)Mo(eta(3)-Ph(2)SiCCR) (3a, R = (t)Bu; 3b, R = (i)Pr)通过 Cp*(CO)(2)(MeCN)MoMe (1) 与炔基硅烷 HPh(2)SiC[三键]CR 的反应合成。3a 和 3b 的结构通过核磁共振光谱和 X 射线晶体学进行了充分表征。3a 与 MeOH 在室温下反应得到稳定的四元金属环 Cp*(CO)(2)MoC(=CH(t)Bu)SiPh(2)OMe (5a)，而 3b 的相应反应导致eta(3)-烯丙基复合物 Cp*(CO)(2)Moeta(3)-(MeOPh(2)Si)HCCHCMe(2)} (7) 通过 Cp*(CO)(2) 的形成MoC(=CH(i)Pr)SiPh(2)OMe (5b)。
• η:η-Alkynyl-Bridged W−Si Complexes:  Formation, Structure, and Reaction with Acetone
  作者：Hiroyuki Sakaba、Mako Yoshida、Chizuko Kabuto、Kuninobu Kabuto

  DOI：10.1021/ja050441o

  日期：2005.5.25

  Reactions of (eta5-C5Me4R)(CO)2(MeCN)WMe (R = Me, Et) with HPh2SiCCtBu gave the novel alkynyl-bridged W-Si complexes, (eta5-C5Me4R)(CO)2W(mu-eta1:eta2-CCtBu)(SiPh2) (R = Me, Et), whose alkynyl ligands bridge the tungsten and silicon atoms in an eta1:eta2-coordination mode. The structures of these complexes were fully characterized, including X-ray crystallography. Treatment of (eta5-C5Me5)(CO)2W(mu-eta1:eta2-CCtBu)(SiPh2) with acetone resulted in acetone insertion into the silicon-alkynyl linkage followed by intramolecular C-H activation of the tBu group to give the chelate-type alkyl-alkene complex, (eta5-C5Me5)(CO)2W(eta1:eta2-CH2CMe2C=CHSiPh2OCMe2).
• Hydrosilylation and Hydrogermylation of CO ₂ and CS ₂ by Al and Ga Functionalized Silanes and Germanes – Cooperative Reactivity with Formation of Silyl Formates and Disilylacetals
  作者：Michael Tolzmann、Lina Schürmann、Alexander Hepp、Werner Uhl、Marcus Layh

  DOI：10.1002/ejic.202000723

  日期：2020.11.15

  alkynylelement hydrides iPr2E(H)–C≡C‐tBu (1; E = Si, Ge) with R2M–H [M = Al, Ga; R = tBu, CH(SiMe3)2] afforded in moderate yields the Al and Ga functionalized alkenylsilanes and ‐germanes iPr2E(H)C(MR2)=CH‐tBu (2). The air and moisture sensitive Al compounds reacted with CO2 under mild conditions (room temperature, 1 bar) to yield the formates [iPr2EC(AlR2)=C(H)–tBu]O2CH (3) by C=O insertion into the E–H bond and

  所述alkynylelement氢化物的Hydrometallation我镨2 E（2H）-C≡C-吨卜（1 ; E =硅，锗），其中R 2 M-H [M =铝，镓; R =吨卜，CH（森达3）2 ]在中等产率的Al和Ga官能alkenylsilanes和得到-germanes我镨2 E（H）C（MR 2）= CH-吨BU（2）。空气和湿气敏感的Al化合物在温和的条件下（室温，1 bar）与CO 2反应生成甲酸酯[ i Pr 2 EC（AlR 2）= C（H）– t通过C = O插入E–H键和第二个O原子与铝的配位来生成Bu] O 2 CH（3）。乙缩醛MeAl [C（Si i Pr 2）= CH- t Bu] 2 O 2 CH 2（4a）作为独特的副产物获得。路易斯酸较少的酸性Ga化合物2c即使在较高的温度和压力下也不会与CO 2反应。与CS 2反应生成二硫缩醛[ i Pr 2 EC（M
• Reactions of Tungsten Acetylide–Silylene Complexes with Pyridines: Direct Observation of Silylene/Silyl Migration in Tungsten Acetylide and Carbyne/Vinylidene Frameworks
  作者：Hiroyuki Sakaba、Hiroyuki Oike、Yasuhiro Arai、Eunsang Kwon

  DOI：10.1021/om300772c

  日期：2012.12.10

  Reaction of acetylide-silylene complex Cp*-(CO)(2)W(SiPh2)((CCBu)-Bu-t) (1a) with 4-(dimethylamino)-pyridine (DMAP) gave an equilibrium mixture of DMAP-stabilized silylene acetylide complexes trans- and cis-Cp*-(CO)(2)W(SiPh2 center dot DMAP)((CCBu)-Bu-t) (trans-4 and cis-4). The corresponding reaction using Cp*(CO)(2)W(SiPh2)(CCSiMe3) (2) produced the novel DMAP-coordinated silenylcarbyne/silylvinylidene complex Cp*(CO)(2)W[CC(SiPh2 center dot DMAP)(SiMe3)] (6a) as a major product, which was equilibrated with trans- and cis-Cp*(CO)(2)W(SiPh2 center dot DMAP)(CCSiMe3) (trans-5a and cis-5a) via silylene/silyl migration. The novel structures of cis-4 and 6a were revealed by X-ray crystallography. A mixture of 2 and pyridine exhibited interesting temperature-dependent NMR spectral changes, indicating the formation of trans- and cis-Cp*(CO)(2)W(SiPh2 center dot py)(CCSiMe3) (trans-5b and cis-5b) and Cp*(CO)(2)W[CC(SiPh2 center dot py)(SiMe3)] (6b) at low temperature, while a mixture of la and pyridine showed no such spectral changes.