[bis(2-diphenylphosphinoethyl)phenylphosphine]chloronickel(II) tetraphenylborate | 40326-49-6

• 英文名称: [bis(2-diphenylphosphinoethyl)phenylphosphine]chloronickel(II) tetraphenylborate
• 英文别名: [NiCl(bis(2-diphenylphosphinoethyl)phenylphosphine)](tetraphenylborate)；(NiCl((Ph2PCH2CH2)2PPh))BPh4；[NiCl(PhP(C2H4PPh2)2)]BPh4；(NiCl(triphos))BPh4；[NiCl(triphos)]BPh4
• CAS: 40326-49-6
• 化学式: C₂₄H₂₀B*C₃₄H₃₃ClNiP₃
• 分子量: 947.934
• InChiKey: RWNFWHVYKFSIQT-UHFFFAOYSA-M

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：

  [bis(2-diphenylphosphinoethyl)phenylphosphine]chloronickel(II) tetraphenylborate 在 2,6-二甲基吡啶 作用下， 以 甲醇 、 乙腈 为溶剂， 生成
  参考文献：
  名称：

  Slow proton transfer to coordinated carboxylates: studies on [Ni(O₂CR){PhP(CH₂CH₂PPh₂)₂}]⁺ (R = Et or Ph)

  摘要：

  The reactions between [Ni(O2CR)(triphos)](+) (R = Et or Ph, triphos = PhP(CH2CH2PPh2)(2)) and mixtures of lutH(+) and lut (lut = 2,6-dimethylpyridine) have been studied in MeCN at 25.0 degrees C using stopped-flow spectrophotometry. The kinetics and spectroscopic changes indicate an equilibrium reaction, presumably involving protonation of an oxygen site (the only sites on the complex containing lone pairs of electrons). Proton transfer is slow and comparison of the kinetic data shows that the rates are insensitive to the R substituent. Using the kinetic data, the pK(a)s of [Ni(HO2CR)(triphos)](2+) (pK(a) = 14.5) have been calculated showing that when coordinated to the {Ni(triphos)}(2+) site, RCO2H is about 8 pK(a) units more acidic than the free acid. Comparison of the kinetic results on the reactions of [Ni(O2CR)(triphos)](+) with mixtures of lutH(+) and lut and those of the analogous [Ni(S2CR)(triphos)](+) show that protonation at oxygen is at least 7.6 x 10(3) times faster than to sulfur, and the coordinated carboxylic acid is ca. 8 pK(a) units less acidic than the corresponding coordinated carboxydithioic acid.

  DOI：

  10.1080/00958972.2015.1047773
• 作为产物：
  描述：

  盐酸 、 [Ni(η2-CH2C6H4Me)(PhP(C2H4PPh2)2)]BPh4 以 乙腈 为溶剂， 生成 [bis(2-diphenylphosphinoethyl)phenylphosphine]chloronickel(II) tetraphenylborate
  参考文献：
  名称：

  Synthesis of [Ni(η2-CH2C6H4R-4){PPh(CH2CH2PPh2)2}]+ (R=H, Me or MeO) and protonation reactions with HCl

  摘要：

  The complexes [Ni(eta(2)-CH2C6H4R-4)(triphos)]BPh4 {R = H, Me or MeO; triphos = PhP(CH2CH2PPh2)(2)} have been prepared and characterised by spectroscopy and X-ray crystallography. In all cases the coordination geometry of the nickel is best described as square-planar with an eta(2)-benzyl ligand occupying one of the positions. The orientation of the eta(2)-benzyl ligand is dictated by the steric restrictions imposed by the phenyl groups on the triphos ligand, so that the phenyl group on the unique secondary phosphorus and the aromatic group of the benzyl ligand (which are trans to one another) are oriented in the same direction. [Ni(eta(2)-CH2C6H4R-4)(triphos)](+) react with an excess of anhydrous HCl in MeCN to form [NiCl(triphos)](+) (characterised as the [BPh4](-) salt by X-ray crystallography) and the corresponding substituted toluene. The kinetics of the reaction of all [Ni(eta(2)-CH2C6H4R-4)(triphos)](+) and HCl in the presence of Cl- have been determined using stopped-flow spectrophotometry. All reactions exhibit a first-order dependence on the concentration of complex and a first-order dependence on the ratio [HCl]/[Cl-]. Varying the 4-R-substituent on the benzyl ligand shows that electron-withdrawing substituents facilitate the rate of the reaction. It is proposed that the mechanism involves initial rapid protonation at the nickel to form [NiH(eta(2)-CH2C6H4R-4)(triphoS)](2+), followed by intramolecular proton migration from nickel to carbon to yield the products. (c) 2005 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2005.01.034

文献信息

• Mechanism of proton transfer to coordinated thiolates: encapsulation of acid stabilizes precursor intermediate
  作者：Ahmed Alwaaly、William Clegg、Ross W. Harrington、Athinoula L. Petrou、Richard A. Henderson

  DOI：10.1039/c5dt01716e

  日期：——

  Hydrogen bonded intermediate in protonation of [Ni(thiolate)(triphos)]⁺ by 2,6-lutidinium is stabilized by encapsulation of the acid by phenyl groups of triphos.

  2,6-lutidinium通过苯基三磷酰基团封装酸，稳定了[Ni(thiolate)(triphos)]⁺质子化过程中氢键结合的中间体。

• Proton Transfer to Nickel−Thiolate Complexes. 2. Rate-Limiting Intramolecular Proton Transfer in the Reactions of [Ni(SC₆H₄R-4)(PhP{CH₂CH₂PPh₂}₂)]⁺ (R = NO₂, Cl, H, Me, or MeO)
  作者：Valerie Autissier、Pedro Martin Zarza、Athinoula Petrou、Richard A. Henderson、Ross W. Harrington、William C. Clegg

  DOI：10.1021/ic0303237

  日期：2004.5.1

  of [Ni(SC(6)H(4)R-4)(triphos)](+) (triphos = PhP[CH(2)CH(2)PPh(2)](2); R = NO(2), Cl, H, Me, or MeO) by [lutH](+) (lut = 2,6-dimethylpyridine) to form [Ni(S(H)C(6)H(4)R-4)(triphos)](2+) is an equilibrium reaction in MeCN. Kinetic studies, using stopped-flow spectrophotometry, reveal that the reactions occur by a two-step mechanism. Initially, [lutH](+) rapidly binds to the complex (K(2)(R)) in an interaction

  [Ni（SC（6）H（4）R-4）（triphos）]（+）的质子化（triphos = PhP [CH（2）CH（2）PPh（2）]（2）; R = NO （2），Cl，H，Me或MeO）由[lutH]（+）（lut = 2,6-二甲基吡啶）形成[Ni（S（H）C（6）H（4）R-4） （triphos）]（2+）是MeCN中的平衡反应。使用停止流分光光度法的动力学研究表明，反应是通过两步机理进行的。最初，[lutH]（+）在相互作用中迅速结合到配合物（K（2）（R））上，这种相互作用可能涉及酸与硫的氢键结合。由于电子和空间因素，随后分子内质子从[lutH]（+）转移到硫（k（3）（R））的速度很慢。[Ni（SC（6）H（4）R-4）（triphos）]（+）的X射线晶体结构（R = NO（2），H，Me或MeO）显示所有描述都最好作为方平面复合体，三价配体的苯基取代基对空间上要求硫的[
• Mechanisms and rates of proton transfer to coordinated carboxydithioates: studies on [Ni(S₂CR){PhP(CH₂CH₂PPh₂)₂}]⁺ (R = Me, Et, Buⁿ or Ph)
  作者：Ahmed Alwaaly、William Clegg、Richard A. Henderson、Michael R. Probert、Paul G. Waddell

  DOI：10.1039/c4dt03543g

  日期：——

  spanning axial and equatorial sites, the other axial site being occupied by the central phosphorus of triphos. The reactions of [Ni(S2CR)(triphos)]+ with mixtures of HCl and Cl− in MeCN to form equilibrium solutions containing [Ni(SH(S)CR)(triphos)]2+ have been studied using stopped-flow spectrophotometry. The kinetics show that proton transfer is slower than the diffusion-controlled limit and involves

  已经制备并表征了配合物[Ni（S 2 CR）（triphos）] BPh 4（R = Me，Et，Bu n或Ph;三光子= PhP CH 2 CH 2 PPh 2 } 2）。X射线晶体学（对于R = Et，Ph，C 6 H 4 Me-4，C 6 H 4 OMe-4和C 6 H 4Cl-4）表明，阳离子中五配位镍的几何形状最好描述为扭曲的三角双锥体，其包含二齿的羧基二硫代酸酯配体，两个硫原子跨越轴向和赤道位点，另一个轴向位点被中心占据。三ho磷。的[镍（S反应2 CR）（三膦）] +用HCl和Cl的混合物-含有形式平衡的解决方案在MeCN [镍（SH（S）CR）（三膦）] 2+已经研究了使用stopped-流动分光光度法。动力学表明，质子传递比扩散控制的极限慢，并且涉及至少两个耦合的平衡。第一步涉及[Ni（S 2 CR）（triphos）]之间的快速关联+和HCl形成氢键结合的前体[Ni（S
• Kinetic Evidence for Intramolecular Proton Transfer Between Nickel and Coordinated Thiolate
  作者：William Clegg、Richard A Henderson*

  DOI：10.1021/ic0104306

  日期：2002.3.1

  [Ni(YR)(triphos)]BPh(4) (Y = S, R = Ph or Et or Y = Se, R = Ph; triphos = (Ph(2)PCH(2)CH(2))(2)PPh) have been prepared and characterized, and the X-ray crystal structure of [Ni(SPh)(triphos)]BPh(4) has been solved. In MeCN, [Ni(YR)(triphos)](+) are protonated by [lutH](+) (lut = 2,6-dimethylpyridine) to give [Ni(YHR)(triphos)](2+). Studies on the kinetics of these equilibrium reactions reveal an unexpected difference

  配合物[Ni（YR）（triphos）] BPh（4）（Y = S，R = Ph或Et或Y = SE，R = Ph;三光=（Ph（2）PCH（2）CH（2））制备并表征了（2）PPh，并且已经解决了[Ni（SPh）（triphos）] BPh（4）的X射线晶体结构。在MeCN中，[Ni（YR）（triphos）]（+）被[lutH]（+）质子化（lut = 2,6-二甲基吡啶）得到[Ni（YHR）（triphos）]（2+）。对这些平衡反应动力学的研究表明，[Ni（SPh）（triphos）]（+）和[Ni（SEt）（triphos）]（+）的反应性存在出乎意料的差异。在两种情况下，反应均显示出对复合物浓度的一级依赖性。当R = Ph时，对[lutH（+）]和lut浓度的依赖性为k（obs）= k（1）（Ph）[lutH（+）] + k（-1）（Ph）[ lut]，这是典型的平衡反应，其中
• Basicities of Nickel and Allyl in [Ni(η³-C₃H₅)(PhP(CH₂CH₂PPh₂)₂]⁺ and Comparison of the Effects of Allyl and Methyl on the Basicity of Nickel
  作者：William Clegg、Graham Cropper、Richard A. Henderson、Christopher Strong、Benjamin Parkinson

  DOI：10.1021/om0100535

  日期：2001.6.1

  Kinetic studies on the reaction between [Ni(eta (3)-C3H5)(triphos)](+) (triphos = Ph2PCH2CH2}(2)-PPh) and [lutH](+) (lut = 2,6-dimethylpyridine) in MeCN show that initial protonation of the nickel or allyl is followed by equilibration of the proton between the two sites. Analysis of the data allows calculation of the basicities of the nickel and allyl sites. This, together with earlier work on [NiMe(triphos)](+), shows the nickel site is (2.5-79) x 10(6) times more basic when coordinated to allyl than to methyl.