H-Ga(CMe₃)₂ | 378795-11-0

• 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: H-Ga(CMe₃)₂
• 英文别名: ditert-butylgallane
• CAS: 378795-11-0
• 化学式: C₈H₁₉Ga
• 分子量: 184.962
• InChiKey: YHOOQLDZNGXWME-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.86
• 重原子数：
  9.0
• 可旋转键数：
  0.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  H-Ga(CMe₃)₂ 以 正己烷 、 甲苯 为溶剂， 反应 352.0h， 生成
  参考文献：
  名称：

  Aluminum and Gallium Hydrazides as Active Lewis Pairs: Cooperative C–H Bond Activation with H–C≡C–Ph and Pentafluorobenzene

  摘要：

  Hydroalumination or hydrogallation of a sterically encumbered hydrazone, H10C5N-N=C(C9H14) (NC5H10 = piperidine, C(C9H14) = 2-adamantdiy1), afforded hydrazides that, depending on the steric shielding by the substituents at the metal atoms, had different molecular structures. While both di(tert-butyl)metal derivatives (1a, 1b) are monomeric in the solid state with highly strained MN2 heterocycles (M = Al, Ga), the dimethylmetal compounds (1c, 1d) are dimeric with M2N2 heterocycles and exocyclic N-N bonds. The latter compounds are highly dynamic in solution. 1d crystallized as a mixture of cis- and trans-isomers as detected by crystal structure determinations. These compounds react as active Lewis pairs by their specific donor acceptor functionality and are able to activate C-H bonds of moderately acidic substrates. Reaction of la (M = Al) with H-C C-C6H5 afforded by C-H bond activation and release of H-CMe3 trialkynyl compound 4, in which three alkynyl groups and a neutral hydrazine ligand are bound to Al. 1b (M = Ga) gave only the known dimeric monoalkynyl derivative [(Me3C)(2)Ga-C C-C6H5](2) (5b). The sterically less shielded dimethyl compounds 1c and 1d similarly yielded trialkynylmetal compounds by methane and hydrogen elimination. In this case a hydrazone ligand is coordinated to the metal atoms. 1d reacted with pentafluorobenzene in an unprecedented reaction to yield a diaryl-methylgallium compound with the metal atom bound to two electron-withdrawing groups and a hydrazone ligand completing the coordination sphere of Ga.

  DOI：

  10.1021/acs.organomet.6b00658

文献信息

• Alkenyl‐Alkynylgermanes Functionalised by Lewis Acids: Intramolecular Aluminium– and Gallium–Alkyne Interactions and Potential Ge–C Bond Activation
  作者：Werner Uhl、Stefan Pelties、Martina Rohling、Jens Tannert

  DOI：10.1002/ejic.201402132

  日期：2014.6

  reduction of one of their C≡C triple bonds. The alkenyl groups have a cis arrangement of H and Al or Ga atoms across the C=C double bonds, which reflects the kinetically favoured situation. The cis/trans isomerisation is probably prevented from yielding thermodynamically favoured trans isomers; this is a result of an intramolecular bonding interaction between the α-carbon atoms of the remaining ethynyl

  使用等摩尔量的二（叔）二乙炔（R1）2Ge（C≡C–R2）2（R1 = C6H5、CH3；R1–R1 = C6H4– ；R2 = 、CMe3、nBu、 ）的处理-丁基)铝或-氢化镓，R2E–H (E = Al, Ga)，得到混合的烯基-炔基锗烷，(R1)2Ge(C≡C–R2)[CE(CMe3)2}=C(H) )–R2]，通过还原其中一个 C≡C 三键。烯基在 C=C 双键上具有 H 和 Al 或 Ga 原子的顺式排列，这反映了动力学有利的情况。顺式/反式异构化可能会阻止产生热力学有利的反式异构体；这是剩余乙炔基的α-碳原子与配位不饱和金属原子之间分子内键合相互作用的结果。
• Hydroalumination versus Deprotonation of Alkynes with Sterically Demanding Substituents
  作者：Werner Uhl、Marcus Layh、Ines Rhotert、Agnes Wollschläger、Alexander Hepp

  DOI：10.5560/znb.2013-3070

  日期：2013.6.1

  Treatment of sterically highly shielded terminal alkynes, H-C≡C-aryl, with dialkylaluminium and dialkylgallium hydrides, R₂E-H, afforded by hydrogen release dimeric dialkylelement alkynides with a four-membered E₂C₂ heterocycle independent of the bulk of the aryl groups. A rare example of a monomeric alkynylaluminium compound was only obtained with very bulky CH(SiMe₃)₂ groups attached to the metal atoms and by salt elimination reaction. The steric shielding by the bulky aryl groups did not prevent condensation reactions. Hydroalumination of 1-(trimethylsilyl)-2-(2,6- dimethylphenyl)ethyne using Me₂Al-H resulted in a divinyl compound by elimination of trimethylaluminium

  摘要 用二烷基铝和二烷基镓氢化物 R2E-H 处理具有高度立体屏蔽的 H-C≡C-芳基末端炔，通过氢释放可得到具有独立于芳基基团的四元 E2C2 杂环的二聚二烷基元素炔。只有在金属原子上连接了非常笨重的 CH(SiMe3)2 基团，并通过消盐反应，才能得到单体炔铝化合物的罕见实例。笨重芳基的立体屏蔽并不能阻止缩合反应。使用 ME2Al-H 对 1-(三甲基硅基)-2-(2,6- 二甲基苯基)乙炔进行氢化氨化，通过消除三甲基铝，可得到二乙烯基化合物。
• 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
• Two Different Structural Motifs Observed for Dimeric Dialkylaluminum and Dialkylgallium Alkynides [R2E-C?C-C6H5]2
  作者：Werner Uhl、Frank Breher、Sima Haddadpour、Rainer Koch、Madhat Matar

  DOI：10.1002/zaac.200400150

  日期：2004.10

  interestingly, different types of molecular structures were observed depending on the steric demand of the substituents terminally attached to the aluminum or gallium atoms. The small methyl substituents gave structures in which the aluminum or gallium atoms seemed to be side-on coordinated by the C≡C triple bonds of almost linear E-C≡C groups. In contrast, the more bulky tert-butyl groups forced an arrangement

  二烷基铝和二烷基镓炔化物 [R2E-C≡CR']2 (R = Me, CMe3; E = Al, Ga; R' = Ph) 含有连接到其中心铝或镓原子的 C≡C 三键，很容易通过以下方法获得：二烷基元素氯化物与锂炔化物的反应或通过用二烷基铝或氢化二烷基镓处理相应的炔烃RC≡CH。第一个反应有利于 LiCl 的沉淀，第二个反应有利于形成元素氢。所有产物都形成二聚体，其中炔基的碳负离子碳原子采用桥接位置，但有趣的是，根据末端连接到铝或镓原子的取代基的空间需求，观察到不同类型的分子结构。小的甲基取代基给出的结构中铝或镓原子似乎是由几乎线性的 EC≡C 基团的 C≡C 三键配位的。相反，体积更大的叔丁基迫使C≡C三键垂直于分子的EE轴的排列。通过量子化学计算分析了不同的键合模式。Unterschiedliche Struktureinheiten in dimeren 二烷基铝-和二烷基镓烷基化物
• Hydroalumination and Hydrogallation of 1,2-Bis(trimethylsilylethynyl)benzene: Formation of Molecular Capsules and C−C Bond Activation
  作者：Werner Uhl、Alexander Hepp、Hauke Westenberg、Sarina Zemke、Ernst-Ulrich Würthwein、Johannes Hellmann

  DOI：10.1021/om901058a

  日期：2010.3.22

  spectroscopic methods. Addition of the Lewis base ethyldimethylamine initiated condensation reactions which gave cage compounds (3 and 4) by the release of the corresponding tri-tert-butyl element derivatives. These cages contain two aluminum or gallium atoms which are bridged by three 1,2-bis(trimethylsilylethenyl)benzene spacers to form molecular capsules. The metal atoms are further coordinated by terminal

  的1,2-双处理（三甲基硅乙炔基）苯与二叔-butylaluminum和二-叔-butylgallium氢化物，得到简单的加成产物1,2 - [（ME 3 Si）的（R 2 E）C = C（H） ] 2 C 6 H 4（R = CMe 3； E = Al（1），Ga（2）），不能以纯结晶形式分离，但已通过光谱法明确鉴定。路易斯碱的乙基二甲胺加成发起这给笼化合物（缩合反应3和4通过相应的三-释放）叔丁基元素衍生物。这些笼子包含两个铝或镓原子，它们被三个1,2-双（三甲基甲硅烷基乙烯基）苯间隔基桥接形成分子胶囊。金属原子进一步被末端氨基配位。不能将氨基配体不经分解而从二价铝化合物4中除去，但是在真空下将3（E ＝ Ga）加热至80℃获得了不含配体的镓化合物5。铝化合物的热解1中沸腾Ñ正己烷，得到由三-释放的独特反应叔-butylaluminum和trimethylsilylethyne（dec