N,N-dimethylanilinium tetraphenylborate

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N,N-dimethylanilinium tetraphenylborate
• 英文别名: Ν,Ν-dimethylanilinium tetraphenylborate；dimethylanilinium tetraphenylborate；N,N-dimethylanilinium tetra(phenyl)boron；dimethylphenylammoniumtetra(phenyl)borate；Dimethylphenylammonium tetraphenylborate；dimethyl(phenyl)azanium;tetraphenylboranuide
• 化学式: C₈H₁₂N*C₂₄H₂₀B
• 分子量: 441.424
• InChiKey: VHHRALHDJHADFM-UHFFFAOYSA-O

计算性质

• 辛醇/水分配系数(LogP)：
  3.53
• 重原子数：
  34
• 可旋转键数：
  5
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  4.4
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (eta.5-C5Me5)2ScCH3 、 N,N-dimethylanilinium tetraphenylborate 以 甲苯 为溶剂， 以67%的产率得到decamethylscandocene*BPh4
  参考文献：
  名称：

  裸 (C5Me5)2M 阳离子（M = Sc、Ti 和 V）及其氟芳烃配合物

  摘要：

  合成了三价 3d 金属 Sc、Ti 和 V 的离子茂金属配合物 [Cp*(2)M][BPh(4)](Cp* = C(5)Me(5)) 并在结构上进行了表征。对于 M = Sc，阴离子通过苯基之一与金属中心弱相互作用，但对于 M = Ti 和 V，阳离子是裸露的。它们每个都包含一个强烈扭曲的 Cp* 配体，具有一个 (V) 或两个 (Ti) 激动性 CH...M 相互作用，涉及 Cp*Me 基团。对于 Sc 和 Ti，这些路易斯酸性物质与氟苯和 1,2-二氟苯反应生成 [Cp*(2)M(kappaF-FC(6)H(5))(n)][BPh(4)] ( M = Sc, n = 2; M = Ti, n = 1) 和 [Cp*(2)M(kappa(2)F-1,2-F(2)C(6)H(4))][ BPh(4)]，过渡金属的 kappaF-氟苯和 kappa(2)F-1,2-二氟苯加合物的第一个例子。使用全氟阴离子

  DOI：

  10.1021/ja054544i
• 作为产物：
  描述：

  N,N-二甲基苯胺 、 Dicyclohexyl(phenyl)phosphanium;tetraphenylboranuide 以 四氢呋喃 为溶剂， 生成 苯基二环己基膦 、 N,N-dimethylanilinium tetraphenylborate
  参考文献：
  名称：

  An Acidity Scale for Phosphorus-Containing Compounds Including Metal Hydrides and Dihydrogen Complexes in THF:  Toward the Unification of Acidity Scales

  摘要：

  More than 70 equilibrium constants K between acids and bases, mainly phosphine derivatives, have been measured in tetrahydrofuran (THF) at 20 degrees C by H-1 and/or P-31 NMR. The acids were chosen or newly synthesized in order to cover the, wide pK(a)(THF) range of 5-41 versus the anchor compound [HPCy3]BPh4 at 9.7. These pK(alpha)(THF) values-are approximations to absolute, free ion pK(a)(THF) and are obtained by crudely correcting the observed K for 1:1 ion-pairing effects by use of the Fuoss equation. The acid/base compounds include 14 phosphonium/phosphine couples, 17 cationic hydride/neutral hydride couples, 9 neutral polyhydride/anionic hydride couples, 14 dihydrogen/hydride couples, and 4 other nitrogen- and phosphorus-based acids. The effects on pK(alpha) of the:counterions BAr'(-)(4) and BF4- vs BPh4- and [K(2,2,2-crypt)](+) versus [K(18-crown-6)](+) are found to be minor after correcting for differences in inter-ion distances in the ion-pairs involved. Correlations with nu(M-H) noted here for the first time suggest that destabilization of M-H bonding in the conjugate base hydride is an important contributor to hydride acidity, It appears that Re-H bonding in the anions [ReH6(PR3)(2)](-) is greatly weakened by small increases in the basicity of PR3, resulting in a large increase in the pK(alpha) of the conjugate acid ReH7(PR3)(2) Correlations with other scales allow an estimate of the pK(alpha)(THF) values of more than 1000 inorganic and organic acids, 20 carbonyl hydride complexes, 46 cationic hydrides complexes, and dihydrogen gas. Therefore, many new acid-base reactions can be predicted and known reactions explained. THF, with its low dielectric constant, disfavors the ionization of neutral acids KA over HB+, and therefore separate lines are found for pK(alpha)(THF)(HA) and pK(alpha)(THF)(HB+) when plotted against pK(a)(DMSO) or pK(a)(MeCN). The crystal structure of [Re(H)(2)(PMe3)(5)]BPh4 is reported.

  DOI：

  10.1021/ja994428d

文献信息

• Relative Reactivity of the Metal−Amido versus Metal−Imido Bond in Linked Cp-Amido and Half-Sandwich Complexes of Vanadium
  作者：Marco W. Bouwkamp、Aurora A. Batinas、Peter T. Witte、Ton Hubregtse、Jeroen Dam、Auke Meetsma、Jan H. Teuben、Bart Hessen

  DOI：10.1021/om8003306

  日期：2008.8.1

  be generated as its N,N-dimethylaniline adduct by treatment of the methyl complex with [PhNMe2H][BAr4] (Ar = Ph, C6F5). Instead, the analogous reaction with the linked Cp-amido precursor results in protonation of the imido-nitrogen atom. Sequential cyclometalation of the amide substituents gave cationic imine complexes [(η5-C5H4C2H4NCR′2)V(NH-t-Bu)]+ (R′ = H, Me) and methane. Reaction of cationic [(

  （η的治疗5 -C 5 H ^ 4 c ^ 2 ^ h 4 NR）V（N-吨-Bu）Me（R = Me中，我-Pr）和CPV（N- p -Tol）（N-我-Pr 2）我（CP =η 5 -C 5 H ^ 5）与B（C 6 ˚F 5）3或[PH 3 C] [B（C 6 ˚F 5）4 ]导致形成相应的阳离子，[（η 5 -C 5 H 4 C 2 H 4NR）V（N- t- Bu）] +和[CpV（N- p -Tol ）（N- i -Pr 2）] +。后者也可以通过用[PhNMe 2 H] [BAr 4 ]（Ar = Ph，C 6 F 5）处理甲基络合物而生成为其N，N-二甲基苯胺加合物。相反，与连接的Cp-酰胺基前体的类似反应导致亚氨基-氮原子的质子化。酰胺取代基的序贯环金属化，得到阳离子亚胺配合物[（η 5 -C 5 H ^ 4 c ^ 2 ^ h 4 NCR'2）V（NH- t- Bu）]
• A Cationic Zinc Hydride Cluster Stabilized by an N-Heterocyclic Carbene: Synthesis, Reactivity, and Hydrosilylation Catalysis
  作者：Arnab Rit、Alessandro Zanardi、Thomas P. Spaniol、Laurent Maron、Jun Okuda

  DOI：10.1002/anie.201408346

  日期：2014.11.24

  The trinuclear cationic zinc hydride cluster [(IMes)3Zn3H4(THF)](BPh4)2 (1) was obtained either by protonation of the neutral zinc dihydride [(IMes)ZnH2]2 with a Brønsted acid or by addition of the putative zinc dication [(IMes)Zn(THF)]2+. A triply bridged thiophenolato complex 2 was formed upon oxidation of 1 with PhSSPh. Protonolysis of 1 by methanol or water gave the corresponding trinuclear dicationic

  三核阳离子氢化锌簇[（IMes）3 Zn 3 H 4（THF）]（BPh 4）2（1）是通过用Brønsted酸将中性二氢化锌[（IMes）ZnH 2 ] 2质子化而获得的。通过添加假定的锌指示剂[（IMes）Zn（THF）] 2+。三重桥接thiophenolato复杂2是经氧化而形成的1与PHS  SPh上。甲醇或水对1进行质子分解，得到相应的三核双效衍生物。在环境温度下1催化醛，酮和腈的氢化硅烷化。当使用（EtO）3 SiH时，二氧化碳在强迫条件下也被氢化硅烷化，从而得到甲硅烷基甲酸酯为主要产物。
• Neutral and Cationic Vanadium(III) Alkyl and Allyl Complexes with a Cyclopentadienyl-amine Ancillary Ligand
  作者：Guohua Liu、Dirk J. Beetstra、Auke Meetsma、Bart Hessen

  DOI：10.1021/om049660t

  日期：2004.8.1

  The (N,N-dimethylaminoethyl)cyclopentadienyl vanadium(III) complex [η5,η1-C5H4(CH2)2NMe2]VCl2(PMe3) (1), in which the pendant amine is coordinated to the metal center, was prepared by the reaction of VCl3(PMe3)2 with Li[C5H4(CH2)2NMe2] in THF. Reaction of 1 with 2 equiv of MeLi yields [η5-C5H4(CH2)2NMe2]VMe2(PMe3)2 (2), in which the amine is released in favor of the binding of a second phosphine. Compound

  的（Ñ，Ñ二甲基氨基乙基）环戊二烯基钒（III）络合物[η 5，η 1 -C 5 ħ 4（CH 2）2 NME 2 ]的VCl 2（PME 3）（1），其中，所述侧胺配位通过使VCl 3（PMe 3）2与Li [C 5 H 4（CH 2）2 NMe 2 ]在THF中反应，制备到金属中心的化合物。的反应1与2当量的MeLi产量[η5 -C 5 H 4（CH 2）2 NMe 2 ] VMe 2（PMe 3）2（2），其中胺的释​​放有利于第二膦的结合。化合物2下进行反应以[PhNMe 2 H] [BPH 4 ]，以形成离子配合物[η 5，η 2 -C 5 ħ 4（CH 2）2 N（Me）的CH 2 ] V（PME 3）2 } [ BPh 4 ]（3），其中NMe 2侧链官能团的甲基被金属化，甲烷为2当量。的反应1与烯丙基氯化镁产率[η 5 -C 5 H ^ 4（CH 2）2 NME 2 ] V（η
• Bimetallic complexes III. Synthesis and reactions of C5H4PPh2-bridged zirconium-molybdenum and zirconium-tungsten complexes
  作者：W.A Schenk、T Gutmann

  DOI：10.1016/s0022-328x(97)00324-0

  日期：1997.10

  products [(Cp′2ZrMe)2(μ-O)](7). Cp′2Zr(SR)2 (R Me (8a), Ph (8b), CH2H4Cl (8c)). Cp′2Zr(Me)OR (R  CH2CF3 (9a), t-Bu (9b), and Cp′2Zr(Cl)Ot-Bu (10) were obtained. Treatment of [Mo(CO)4(norabornadiene )]with either 2, 4 or 9a gives the bis-Cp′ bridged binuclear tetracarbonyl complexes [Cp′2Zr(Me)(X)Mo(CO)4] (X  Cl (11), Ph (12). OCH2CF3 (13). Binuclear complexes [Cp′2Zr(X)(μ-Cl)M(CO)3] (X  Me, M  Mo, W (14a

  描述了具有桥连的C 5 H 4 PPh 2配体（以下简称为Cp'）的双金属Zr andMo和Zr biW配合物的合成和反应。Cp的反应' 2的ZrCl 2（1用有机锂或格氏试剂）得到的Cp' 2 ZRR 2（R我（3）。PC 6 ħ 4 CH 3（5）。CH 2森达3（6）），而与阿尔梅3单交换产物CP' 2的Zr（CI）我（2） 形成了。苯基转换2到CP' 2的Zr（ME）PH（4）。从1-3的取代产物[（CP' 2 ZrMe）2（μ-O）]（7）。CP' 2的Zr（SR）2（RMe（图8a）中，Ph（图8b），CH 2 ħ 4氯（8C））。CP' 2的Zr（Me）或（RCH 2 CF 3（图9a），吨-Bu（图9b），和CP' 2的Zr（CL）O吨-Bu（10）。的治疗[沫（CO）4（norabornadiene）]与任2,4或图9a给出了双-Cp'桥连的双核四羰配合物[CP'
• Neutral and cationic yttrium alkyl complexes with linked 1,4,7-triazacyclononane-amide monoanionic ancillary ligands: synthesis and catalytic ethene polymerisation
  作者：Sergio Bambirra、Daan van Leusen、Auke Meetsma、Bart Hessen、Jan H. Teuben

  DOI：10.1039/b101012n

  日期：——

  Yttrium dialkyl complexes [N,N′-R2-tacn-N″-(CH 2)2NBut]Y(CH2SiMe3) 2 (R = Me, Pri; tacn = 1,4,7-triazacyclononane) were prepared; when activated with [PhNMe2H][B(C6F5)4] these complexes form cationic alkyl species that are active ethene polymerisation catalysts.

  制备了二烷基钇配合物[N,N'-R2-tacn-N”-(CH 2)2NBut]Y(CH2SiMe3) 2 (R = Me, Pri; tacn = 1,4,7-三氮杂环壬烷)；当用 [PhNMe2H][B(C6F5)4] 活化时，这些配合物形成阳离子烷基物质，它们是活性乙烯聚合催化剂。