[o,o-C₆H₃(CH₂NMe₂)₂]BiCl₂ | 144501-68-8

• 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: [o,o-C₆H₃(CH₂NMe₂)₂]BiCl₂
• 英文别名: Cl2Bi[O2C(C6H2tBu2-3-5-O-4)-κ2O,O′]；2,6-(Me₂NCH₂)₂C₆H₃BiCl₂；2,6-bis{(dimethylamino)methyl}phenyldichlorobismuthine；[(C6H3-2,6-(CH2NMe2)2)BiCl2]；1-[2-dichlorobismuthanyl-3-[(dimethylamino)methyl]phenyl]-N,N-dimethylmethanamine
• CAS: 144501-68-8
• 化学式: C₁₂H₁₉BiCl₂N₂
• 分子量: 471.183
• InChiKey: MJTHTSNVKKVJFU-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  -4.76
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [o,o-C₆H₃(CH₂NMe₂)₂]BiCl₂ 以 四氢呋喃 为溶剂， 反应 7.0h， 生成 2a-chloro-2a-(3,5-di-tert-butyl-4-((trimethylsilyl)oxy)phenyl)-2,2,3,3-tetramethyl-2,2a,3,4-tetrahydro-1H-2,3-diaza-2a5-bismacyclopenta[hi]indene-2,3-diium
  参考文献：
  名称：

  Insertion of CO₂ and COS into Bi–C Bonds: Reactivity of a Bismuth NCN Pincer Complex of an Oxyaryl Dianionic Ligand, [2,6-(Me₂NCH₂)₂C₆H₃]Bi(C₆H₂^tBu₂O)

  摘要：

  The reactivity of the unusual oxyaryl dianionic ligand, ((C6H2Bu2)-Bu-t-3,5-O-4)(2-), in the Bi3+ NCN pincer complex Ar'Bi((C6H2Bu2)-Bu-t-3,5-O-4), 1, [Ar' = 2,6-(Me2NCH2)(2)C6H3] has been explored with small molecule substrates and electrophiles. The first insertion reactions of CO2 and COS into Bi-C bonds are observed with this oxyaryl dianionic ligand complex. These reactions generate new dianions that have quinoidal character similar to the oxyaryl dianionic ligand in 1. The oxyarylcarboxy and oxyarylthiocarboxy dianionic ligands were identified by X-ray crystallography in Ar'Bi[O2C((C6H2Bu2)-Bu-t-3-5-O-4)-kappa O-2,O'], 2, and Ar'B[OSC((C6H2Bu2)-Bu-t-3-5-O-4)-kappa O-2,S], 3, respectively. Silyl halides and pseudohalides, R3SiX (X = Cl, CN, N-3; R = Me, Ph), react with 1 by attaching X to bismuth and R3Si to the oxyaryl oxygen to form Ar'Bi(X)((C6H2Bu2)-Bu-t-3,5-OSiR3-4) complexes, a formal addition across five bonds. These react with additional R3SiX to generate Ar'BiX2 complexes and (R3SiOC6H3Bu2)-Bu-t-2,6. The reaction of 1 with I-2 forms Ar'BiI2 and the coupled quinone, 3,3',5,5'-tetra-tert-butyl-4,4'-diphenoquinone, by oxidative coupling.

  DOI：

  10.1021/ja403133f
• 作为产物：
  描述：

  (2,6-(Me₂NCH₂)₂C₆H₃₎Bi(C₆H₂tBu₂-3,5-O-4) 以 四氢呋喃 为溶剂， 反应 17.5h， 生成 [o,o-C₆H₃(CH₂NMe₂)₂]BiCl₂
  参考文献：
  名称：

  Insertion of CO₂ and COS into Bi–C Bonds: Reactivity of a Bismuth NCN Pincer Complex of an Oxyaryl Dianionic Ligand, [2,6-(Me₂NCH₂)₂C₆H₃]Bi(C₆H₂^tBu₂O)

  摘要：

  The reactivity of the unusual oxyaryl dianionic ligand, ((C6H2Bu2)-Bu-t-3,5-O-4)(2-), in the Bi3+ NCN pincer complex Ar'Bi((C6H2Bu2)-Bu-t-3,5-O-4), 1, [Ar' = 2,6-(Me2NCH2)(2)C6H3] has been explored with small molecule substrates and electrophiles. The first insertion reactions of CO2 and COS into Bi-C bonds are observed with this oxyaryl dianionic ligand complex. These reactions generate new dianions that have quinoidal character similar to the oxyaryl dianionic ligand in 1. The oxyarylcarboxy and oxyarylthiocarboxy dianionic ligands were identified by X-ray crystallography in Ar'Bi[O2C((C6H2Bu2)-Bu-t-3-5-O-4)-kappa O-2,O'], 2, and Ar'B[OSC((C6H2Bu2)-Bu-t-3-5-O-4)-kappa O-2,S], 3, respectively. Silyl halides and pseudohalides, R3SiX (X = Cl, CN, N-3; R = Me, Ph), react with 1 by attaching X to bismuth and R3Si to the oxyaryl oxygen to form Ar'Bi(X)((C6H2Bu2)-Bu-t-3,5-OSiR3-4) complexes, a formal addition across five bonds. These react with additional R3SiX to generate Ar'BiX2 complexes and (R3SiOC6H3Bu2)-Bu-t-2,6. The reaction of 1 with I-2 forms Ar'BiI2 and the coupled quinone, 3,3',5,5'-tetra-tert-butyl-4,4'-diphenoquinone, by oxidative coupling.

  DOI：

  10.1021/ja403133f

文献信息

• Oxidative addition of organic disulfides to low valent N,C,N-chelated organobismuth(I) compound: Isolation, structure and coordination capability of substituted bismuth(III) bis(arylsulfides)
  作者：Petr Šimon、Roman Jambor、Aleš Růžička、Libor Dostál

  DOI：10.1016/j.jorganchem.2013.05.005

  日期：2013.9

  organobismuth(I) [LBi]n compound (not isolated), via reaction of LBiCl2 (1) (where L = [o,o-C6H3(CH2NMe2)2]) with K[B(s-Bu)3H] (K-Selectride), and a set of diorganodisulfides ArSSAr gave organobismuth(III) compounds LBi(SAr)2 2–7 (where Ar = 2-pyridyl (2), 4-metylthiazol-2-yl (3), thiofen-2-yl (4), 4-tert-butyl-1-iso-propyl-1H-imidazol-2-yl (5), 1-phenyl-1H-tetrazol-5-yl (6), 2-aminophenyl (7)). Compounds 2–7

  之间的反应在原位制备的THF溶液Ñ，Ç，Ñ -chelated有机铋（I）[LBI] Ñ化合物（不分离），通过LBiCl的反应2（1）（其中，L = [ Õ，ø -C 6 ħ 3（CH 2 NMe 2）2 ]）与K [B（s -Bu）3 H]（K-Selectride），和一组二有机二硫化物ArSSAr得到有机铋（III）化合物LBi（SAr）2 2 – 7（其中Ar = 2-吡啶基（2），4- metylthiazol -2-基（3），thiofen -2-基（4），4-叔丁基1-异丙基- 1 H ^ -咪唑-2-基（5），1-苯基1 H-四唑-5-基（6），2-氨基苯基（7））。化合物2 - 7通过元素分析的帮助下，进行了表征1 H和13 C NMR光谱和在的情况下，2，3和6由单晶X射线衍射分析的帮助。化合物7在溶液中不稳定，并分解为化合物LBi [S（NH）C6 H 4 ]（8），含有5元的BiSNC
• [2 + 2] Cycloaddition of Carbon Disulfide to NCN-Chelated Organoantimony(III) and Organobismuth(III) Sulfides: Evidence for Terminal Sb−S and Bi−S Bonds in Solution
  作者：Libor Dostál、Roman Jambor、Aleš Růžička、Robert Jirásko、Eva Černošková、Ludvík Beneš、Frank de Proft

  DOI：10.1021/om100613x

  日期：2010.10.25

  sulfides (LMS)2 (L = NCN chelating ligand, C6H3-2,6-(CH2NMe2)2; M = Sb (1), Bi (2)) are dimeric in the solid state. Nevertheless, their monomeric structures with terminal Sb−S and Bi−S bonds present in solution were trapped by [2 + 2] cycloaddition reactions with CS2, giving the molecular trithiocarbonates LMS2C═S (M = Sb (3), Bi (4)). Both compounds were characterized in the solid state by X-ray diffraction

  有机锑（III）和有机铋（III）硫化物（LMS）2（L = NCN螯合配体，C 6 H 3 -2,6-（CH 2 NMe 2）2； M = SB（1），Bi（2） ）是固态的二聚体。然而，它们与存在于溶液端子SB-S和Bi-S键的单体的结构，用CS被困[2 + 2]环加成反应2，赋予分子三硫代碳酸盐LMS 2个C = S（M =锑（3），铋（4））。通过在单晶和粉末材料上的X射线衍射技术以及红外光谱，对这两种化合物进行了固态表征。通过加热到120°C（对于3而言）和160°C（对于4而言）以回收原料硫化物1和2，可以很容易地从三硫代碳酸酯3和4中除去二硫化碳。在溶液中，三硫代碳酸盐3和4与起始硫化物1和2处于平衡状态，但是可以通过添加过量的CS 2将该平衡转变为纯3和4。如1 H NMR光谱所示。
• Probing the Limits of Oxidative Addition of C(sp³)–X Bonds toward Selected <i>N,C,N</i>-Chelated Bismuth(I) Compounds
  作者：Martin Hejda、Robert Jirásko、Aleš Růžička、Roman Jambor、Libor Dostál

  DOI：10.1021/acs.organomet.0c00418

  日期：2020.12.14

  The reactivity of two N,C,N-chelated bismuthinidenes, that is, [2,6-(tBuN═CH)2C6H3]Bi (1) and its metastable analogue [2,6-(Me2NCH2)2C6H3]Bi (2), toward organic substrates containing C(sp3)–X bond (where X = I or OTf) is reported. The aim of this study is to prove the potential of the Bi(I) center in 1 and 2 to participate in an oxidative addition toward C–X bonds under formation of corresponding trivalent

  两个反应性N，C，N -chelated bismuthinidenes，即，[2,6-（吨BuN═CH）2 C ^ 6 ħ 3 ]的Bi（1）及其亚稳态类似物[2,6-（ME 2 NCH 2）2 C 6 H 3 ] Bi（2）朝向含有C（sp 3）–X键（其中X = I或OTf）的有机底物的报道。这项研究的目的是证明Bi（I）中心在1和2中的潜力参与相应的三价铋化合物形成过程中对C–X键的氧化加成反应。检查基材的影响；因此，考虑使用简单的伯烷基（包括氟化的烷基）以及更多的支链底物，以发现这些反应的极限并认识到1和2之间反应性的差异。所有产品均通过高分辨率电喷雾电离质谱（ESI-MS）进行表征。1 H，13 C和19 F NMR光谱；和单晶X射线衍射分析。
• Nitric Oxide Insertion Reactivity with the Bismuth-Carbon Bond: Formation of the Oximate Anion, [ON(C₆H₂<i>t</i>Bu₂O)]⁻, from the Oxyaryl Dianion, (C₆H₂<i>t</i>Bu₂O)²⁻
  作者：Douglas R. Kindra、Ian J. Casely、Joseph W. Ziller、William J. Evans

  DOI：10.1002/chem.201404910

  日期：2014.11.10

  The first example of NO insertion into a BiC bond has been found in the direct reaction of NO with a Bi3+ complex of the unusual (C6H2tBu2‐3,5‐O‐4)2− oxyaryl dianionic ligand, namely, Ar′Bi(C6H2tBu2‐3,5‐O‐4) [Ar′=2,6‐(Me2NCH2)2C6H3] (1). The oximate complexes [Ar′Bi(ONC6H2‐3,5‐tBu2‐4‐O)]2(μ‐O) (3) and Ar′Bi(ONC6H2‐3,5‐tBu2‐4‐O)2 (4) were formed as a mixture, but can be isolated in pure form by reaction

  NO插入Bi的第一示例 C键已经发现NO的与铋的直接反应3+络合物的不寻常的（C的6 ħ 2吨卜2 -3,5-O-4）2-氧基芳基双阴离子配体，即，Ar'Bi（C 6 H ^ 2吨卜2 -3,5-O-4）[中，Ar'= 2,6-（ME 2 NCH 2）2 C ^ 6 ħ 3 ]（1）。肟酸的配合物[Ar'Bi（ONC 6 ħ 2 -3,5-吨卜2 -4-O）] 2（μ-O）（3）和Ar'Bi（ONC 6 H 2 -3,5- t Bu 2-4 -O）2（4）形成混合物，但可以通过NO与Bi 3+的反应以纯净的形式分离出来。复合物中的〔O的2 C（ç 6 ħ 2吨卜2 -3-5-O-4] 2- oxyarylcarboxy二价阴离子，即Ar'Bi〔O 2 C（ç 6 ħ 2吨卜2 -3-5 ‐O‐4）‐κ 2 O，O']。1与Ph 3的反应CSNO生成具有（Ph 3的肟酸产物CS）1-作为辅助配体，（PH
• Hypervalent organobismuth(iii) carbonate, chalcogenides and halides with the pendant arm ligands 2-(Me2NCH2)C6H4 and 2,6-(Me2NCH2)2C6H3
  作者：Hans J. Breunig、Lucia Königsmann、Enno Lork、Mihai Nema、Nicky Philipp、Cristian Silvestru、Albert Soran、Richard A. Varga、Roxana Wagner

  DOI：10.1039/b717127g

  日期：——

  R2BiOH (1) [R = 2-(Me2NCH2)C6H4] and (R2Bi)2O (2) are formed by hydrolysis of R2BiCl with KOH. Single crystals of 2 were obtained by air oxidation of (R2Bi)2. The reaction of R2BiCl and Na2CO3 leads to (R2Bi)2CO3 (3). 3 is also formed by the absorption of CO2 from the air in solutions of 1 or 2 in diethyl ether or toluene. (R2Bi)2S (4) is obtained from R2BiCl and Na2S or from (R2Bi)2 and S8. Exchange reactions between R2BiCl and KBr or NaI give R2BiX [X = Br (5), I (6)]. The reaction of RBiCl2 (7) with Na2S and [W(CO)5(THF)] gives cyclo-(RBiS)2[W(CO)5]2 (8). cyclo-(R′BiS)2 (9) [R′ = 2,6-(Me2NCH2)2C6H3] is formed by reaction of R′BiCl2 and Na2S. The structures of 1–9 were determined by single-crystal X-ray diffraction.

  R₂BiOH (1) [R = 2-(Me₂NCH₂)C₆H₄] 和 (R₂Bi)₂O (2) 通过 R₂BiCl 与 KOH 的水解反应形成。通过空气氧化 (R₂Bi)₂ 获得了2的单晶。R₂BiCl与Na₂CO₃的反应导致 (R₂Bi)₂CO₃ (3) 的形成。3 也可以通过在二乙醚或甲苯中 1 或 2 的溶液中吸收来自空气的 CO₂ 来形成。R₂Bi₂S (4) 是通过 R₂BiCl 和 Na₂S 或从 (R₂Bi)₂ 和 S₈ 反应得到的。R₂BiCl 和 KBr 或 NaI 之间的交换反应给出了 R₂BiX [X = Br (5), I (6)]。RBiCl₂ (7) 与 Na₂S 和 [W(CO)₅(THF)] 的反应生成环状-(RBiS)₂[W(CO)₅]₂ (8)。环状-(R′BiS)₂ (9) [R′ = 2,6-(Me₂NCH₂)₂C₆H₃] 是通过 R′BiCl₂ 和 Na₂S 的反应形成的。1–9 的结构通过单晶 X 射线衍射确定。