1-methyl-3-(2-pyridinylmethyl)-1H-imidazolium tetrafluoroborate | 468081-93-8

• 英文名称: 1-methyl-3-(2-pyridinylmethyl)-1H-imidazolium tetrafluoroborate
• 英文别名: N-methyl-N'-(2-pyridylmethyl)imidazolium tetrafluoroborate；1-(2-pyridylmethyl)-3-methylimidazolium tetrafluoroborate
• CAS: 468081-93-8
• 化学式: BF₄*C₁₀H₁₂N₃
• 分子量: 261.03
• InChiKey: QGTRSGDKXSUFFM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  1-methyl-3-(2-pyridinylmethyl)-1H-imidazolium tetrafluoroborate 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 40.0h， 生成 [Pd{2-Br-4,5-(OCH₂O)C₆HC(H)=NCH₂CH₂NMe₂-C6,N,N}(PyCH₂-ImMe)]BF₄
  参考文献：
  名称：

  用双和三齿席夫碱制备咪唑-2-亚基卡宾钯环 - 光谱、分子结构和 DFT 计算数据分析

  摘要：

  用潜在的多齿咪唑-2-亚基银卡宾配合物处理适当的亚苄基亚胺钯环产生了新的钯有机金属化合物，其中 N-杂环卡宾 (NHC) 与钯中心配位。带有两个卡宾部分的 NHC 在两个金属原子之间显示出桥接配位模式，并且还可能同时显示出桥接/螯合行为。对化合物进行 DFT 计算，通过仔细检查 1H NMR 光谱观察到这些化合物的典型通量行为。13 的晶体和分子结构由 X 射线晶体学确定，并与 14 的计算数据进行对比，以确定后者的通量平衡的最有利配置。

  DOI：

  10.1002/ejic.201501067
• 作为产物：
  描述：

  2-(溴甲基)吡啶氢溴酸盐 在 sodium carbonate 作用下， 以 甲醇 、 水 、 乙腈 为溶剂， 反应 44.0h， 生成 1-methyl-3-(2-pyridinylmethyl)-1H-imidazolium tetrafluoroborate
  参考文献：
  名称：

  用双和三齿席夫碱制备咪唑-2-亚基卡宾钯环 - 光谱、分子结构和 DFT 计算数据分析

  摘要：

  用潜在的多齿咪唑-2-亚基银卡宾配合物处理适当的亚苄基亚胺钯环产生了新的钯有机金属化合物，其中 N-杂环卡宾 (NHC) 与钯中心配位。带有两个卡宾部分的 NHC 在两个金属原子之间显示出桥接配位模式，并且还可能同时显示出桥接/螯合行为。对化合物进行 DFT 计算，通过仔细检查 1H NMR 光谱观察到这些化合物的典型通量行为。13 的晶体和分子结构由 X 射线晶体学确定，并与 14 的计算数据进行对比，以确定后者的通量平衡的最有利配置。

  DOI：

  10.1002/ejic.201501067

文献信息

• An Anion-Dependent Switch in Selectivity Results from a Change of C−H Activation Mechanism in the Reaction of an Imidazolium Salt with IrH₅(PPh₃)₂
  作者：Leah N. Appelhans、Daniele Zuccaccia、Anes Kovacevic、Anthony R. Chianese、John R. Miecznikowski、Alceo Macchioni、Eric Clot、Odile Eisenstein、Robert H. Crabtree

  DOI：10.1021/ja055317j

  日期：2005.11.23

  counteranion along the series Br, BF4, PF6, SbF6 in their ion-paired 2-pyridylmethyl imidazolium salts causes the kinetic reaction products with IrH5(PPh3)2 to switch from chelating N-heterocyclic carbenes (NHCs) having normal C2 (N path) to abnormal C5 binding (AN path). Computational work (DFT) suggests that the AN path involves C-H oxidative addition to Ir(III) to give Ir(V) with little anion dependence. The

  改变 Br、BF4、PF6、SbF6 在其离子对 2-吡啶甲基咪唑鎓盐中的抗衡阴离子会导致与 IrH5(PPh3)2 的动力学反应产物从螯合 N-杂环卡宾 (NHCs) 转换为具有正常 C2 (N路径）到异常 C5 绑定（AN 路径）。计算工作 (DFT) 表明 AN 路径涉及 CH 氧化加成到 Ir(III) 以产生 Ir(V)，而阴离子依赖性很小。相比之下，N 路径通过异裂 CH 激活，质子转移到相邻的氢化物。转移的质子伴随着阴离子耦合质子转移中的抗衡阴离子，导致 N 路径的阴离子依赖性，从而导致 N/AN 选择性。N 路径通过 Ir(III)，而不是 Ir(V)，因为正常 NHC 是比异常 NHC 强得多的供体配体。PGSE NMR 实验支持在反应物和产物中形成离子对。19F,1H-HOESY NMR 实验表明产物的离子对结构与计算预测(ONIOM(B3PW91/UFF))一致。
• Influence of the Anion of the Salt Used on the Coordination Mode of an N-Heterocyclic Carbene Ligand to Osmium
  作者：Miguel Baya、Beatriz Eguillor、Miguel A. Esteruelas、Montserrat Oliván、Enrique Oñate

  DOI：10.1021/om700746h

  日期：2007.12.1

  of the hexahydride OsH6(PiPr3)2 (1) with 1.0 equiv of the BPh4−, BF4−, and Br− salts of 1-(2-pyridylmethyl)-3-methylimidazolium, in tetrahydrofuran under reflux, have been studied. In the three cases, mixtures of the abnormal [OsH(η2-H2)κC5,N-[1-(2-pyridylmethyl)-3-methylimidazol-5-ylidene]}(PiPr3)2]A (A = BPh4 (2a), BF4 (2b), Br (2c)) and normal [OsH(η2-H2)κC2,N-[1-(2-pyridylmethyl)-3-methylimida

  的六氢化职业安全与卫生反应6（P我镨3）2（1）与1.0当量的BPH的4 -，BF 4 -和Br - 1-（2-吡啶基甲基）-3-甲基咪唑的盐，在四氢呋喃下回流，已被研究。在三种情况下，异常[OSH（η的混合物2 -H 2）κ Ç 5，ñ - [1-（2-吡啶基甲基）-3-甲基咪唑-5-亚基]}（P我镨3）2 ] A（A = BPh 4（2a），BF 4（图2b），溴（2C））和正常[OSH（η 2 -H 2）κ Ç 2，Ñ - [1-（2-吡啶基甲基）-3-甲基咪唑-2-亚基]}（P我镨3）获得2 ] A（A ＝ BPh 4（3a），BF 4（3b），Br（3c））异构体。随着使用过的盐的阴离子的配位能力增加，异常异构体的形成速率和异常与正常比率降低。用HBF 4 ·OEt 2或LiBF 4处理2b引起其异构化为3b。阳离子的OSH 3共振的2a和T 1（最小）值的X射线结构支持了这些化合物的氢化物延长的二氢性质。OSH
• Different Reactivities of Pyrid-2-yl- and 6-Picol-2-yl-Functionalized NHC Ligands with [Ru₃(CO)₁₂]: C(sp²)−H and Double C(sp³)−H Bond Activation Reactions
  作者：Javier A. Cabeza、Marina Damonte、Pablo García-Álvarez

  DOI：10.1021/om200109n

  日期：2011.4.25

  [Ru3(κC-MepyCH2ImMe)(CO)11] (2), which is a mere CO-substitution product, or [Ru3(μ-H)2(μ3-κ3C2,N-HCpyCH2ImMe)(CO)8] (3), in which that methyl group has been transformed into a CH fragment through a double C−H bond activation process.

  虽然双齿NHC-吡啶配体1-[（（吡啶-2-基）甲基] -3-甲基咪唑-2-亚甲基（HpyCH 2 ImMe）的直接反应和银介导的反应均导致[Ru 3（μ-H ）（μ-κ 3 ç 2，ñ -pyCH 2 ImMe）（CO）9 ]（1），其中包含一个桥连配体，从吡啶环的金属化发生在6-位置，类似的反应用1- [ （6- picol -2-基）甲基] -3-甲基咪唑烷-2-亚基（MepyCH 2 ImMe），其在相同的配体位置具有甲基，得到任一的[Ru 3（κ ç -MepyCH 2 ImMe）（ CO）11 ]（2），这是一个单纯的CO-取代产物，或的[Ru 3（μ-H）2（μ 3 -κ 3 Ç 2，Ñ -HCpyCH 2 ImMe）（CO）8 ]（3），其中该甲基通过双重CH键活化过程已被转化为CH片段。
• Abnormal Ligand Binding and Reversible Ring Hydrogenation in the Reaction of Imidazolium Salts with IrH₅(PPh₃)₂
  作者：Stephan Gründemann、Anes Kovacevic、Martin Albrecht、Jack W. Faller、Robert H. Crabtree

  DOI：10.1021/ja026735g

  日期：2002.9.1

  We show that imidazolium salts do not always give normal or even aromatic carbenes on metalation, and the chemistry of these ligands can be much more complicated than previously thought. N,N'-disubstituted imidazolium salts of type [(2-py)(CH2)(n)(C3H3N2)R]BF4 react with IrH5(PPh3)(2) to give N,C-chelated products (n = 0, 1; 2-py = 2-pyridyl; C(3)H(3)N2 = imidazolium; R = mesityl, n-butyl, i-propyl, methyl). Depending on the circumstances, three types of kinetic products can be formed: in one, the imidazole metalation site is the normal C2 as expected; in another, the metalation occurs at the abnormal C4 site; and in the third, C4 metalation is accompanied by hydrogenation of the imidazolium ring. The bonding mode is confirmed by structural studies, and spectroscopic criteria can also distinguish the cases. Initial hydrogen transfer can take place from the metal to the carbene to give the imidazolium ring hydrogenation product, as shown by isotope labeling; this hydrogen transfer proves reversible on reflux when the abnormal aromatic carbene is obtained as final product. Care may therefore be needed in the future in verifying the structure(s) formed in cases where a catalyst is generated in situ from imidazolium salt and metal precursor.
• Mono-, Di-, and Trinuclear Luminescent Silver(I) and Gold(I) N-Heterocyclic Carbene Complexes Derived from the Picolyl-Substituted Methylimidazolium Salt:  1-Methyl-3-(2-pyridinylmethyl)-1H-imidazolium Tetrafluoroborate
  作者：Vincent J. Catalano、Adam L. Moore

  DOI：10.1021/ic050604+

  日期：2005.9.1

  The N-heterocyclic carbene (NHC) precursor, 1-methyl-3-(2-pyridinylmethyl)-1H-imidazolium tetrafluoroborate, [HCH(3)im(CH(2)py)]BF4, reacted with AgBF4 in the presence of aqueous NaOH to produce the silver complex [Ag(CH(3)im(CH2PY))(2)]BF4 (1) which was then reacted with Au(tht)Cl to form the corresponding gold(l) complex, [Au(CH(3)im(CH2PY))(2)]BF4 (2). Complex 2 reacted with 1 equiv of AgBF4 to produce the mixed-metal species [AuAg(CH(3)im(CH2PY))(2)](BF4)(2) (3). The reaction of 2 with 1 equiv of Au(tht)Cl followed by metathesis with NaBF4 produces the dimetallic gold complex [Au-2(CH(3)im(CH2PY))(2)](BF4)(2) (4). The reaction of [Ag(CH(3)im(CH2PY))(2)]BF4 (1) with 1 equiv of AgBF4 produces the trinuclear [Ag-3(CH(3)im(CH2PY))(3)(NCCH3)(2)](BF4)(3) (5) complex, which appears to dissociate into a dimetallic complex in solution. Complexes 1-5 were characterized by H-1 NMR, C-13 NMR, UV-vis, luminescence spectroscopy, elemental analysis, mass spectrometry, and X-ray crystallography. The CH(3)im(CH2PY) ligands in 3 are arranged in a head-to-head fashion spanning a Au-Ag separation of 3.0318(5) angstrom with the carbene portion of the ligand remaining coordinated to the Au(I) center. In 4, the ligands are arranged in a head-to-tail fashion with an Au-Au separation of 3.1730(5) angstrom. In 5, the ligands bridge the nearly symmetrical Ag-3 triangular core with short Ag-Ag separations of 2.7765(8), 2.7832(8), and 2.7598(8) angstrom. All of these complexes, including the ligand precursor, are intensely luminescent in solution and the solid state.