(kappa.3-N,N',N''-hydrotris(3,5-dimethylpyrazolyl)borate)Rh(PMe3)(H)2 | 249643-82-1

• 英文名称: (kappa.3-N,N',N''-hydrotris(3,5-dimethylpyrazolyl)borate)Rh(PMe3)(H)2
• 英文别名: (hydrotris(3,5-dimethylpyrazolyl)borate)Rh(H)2(PMe3)；[(tris(3,5-dimethylpyrazolyl)borate)RhH2(PMe3)]；[Rh(tris(3,5-dimethylpyrazolyl)borate)H2(PMe3)]
• CAS: 249643-82-1
• 化学式: C₁₈H₃₃BN₆PRh
• 分子量: 478.19
• InChiKey: WUNHEDSKBDGRJG-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：

  (kappa.3-N,N',N''-hydrotris(3,5-dimethylpyrazolyl)borate)Rh(PMe3)(H)2 以 乙腈 为溶剂， 生成 [(tris(3,5-dimethylpyrazolyl)borate)Rh(CH3)(CN)(PMe3)]
  参考文献：
  名称：

  [Tp'Rh（PR 3）]活化乙腈和丁二腈的CH和C-CN键

  摘要：

  [Tp'Rh（PR 3）]片段，其中Tp'=三（3,5-二甲基吡唑基）硼酸酯，R 3 = Me 3（a）或PhMe 2（b），显示可用于激活乙腈的CH和C-CN键。室温下在乙腈中对Tp'Rh（PR 3）H 2（1a，b）进行光辐照，得到配合物Tp'Rh（PR 3）（CH 2 CN）H（3a，b）。乙腈与[Tp'Rh（PR 3）]由1脱氢生成的片段。Tp'Rh（PME的热反应3）（PH）H（2A）或Tp'Rh（κ 2 -C 6 H ^ 4 -2-PME 2）H（2B）的乙腈在80℃下也导致分别通过还原性消除苯（来自2a）或分子内还原性消除PPhMe 2生成的[Tp'Rh（PR 3）]片段向[Tp'Rh（PR 3）]片段进行氧化加成，分别形成3a和3b配体（来自2b）。加热分离的CH键活化的复合物3a，b在较高温度（100°C）下长时间（≈5天）在乙腈中形成相应的C-CN键活化复合物Tp'Rh（PR

  DOI：

  10.1021/om101002m
• 作为产物：
  描述：

  以 正丁醇 为溶剂， 反应 48.0h， 生成 (kappa.3-N,N',N''-hydrotris(3,5-dimethylpyrazolyl)borate)Rh(PMe3)(H)2
  参考文献：
  名称：

  Tp'Rh（PMe 3）（OR）H中铑-烷氧基键强度的测定

  摘要：

  由热前体Tp'Rh（PMe 3）（CH 3）H生成的活性片段[Tp'Rh（PMe 3）]经过水和醇的氧化加成后得到Tp'Rh类型的OH加合物（PMe 3）（OR）H（R = H，Me，Et，n Pr，n Bu，CH 2 Ph，i Pr，c-戊基，CH 2 CF 3，CH 2 CH 2OH）在环境温度下。这些活化产物消除了苯中的水或醇，从而可以通过使用先前建立的动力学技术确定相对的金属-氧键能。分析相对的M–O键强度和O–H键强度之间的关系显示，脂族醇的R M–O / O–H线性相关，为0.97（3）。两种非常规基材（R = CH 2 CF 3，CH 2 CH 2OH）均具有比该趋势所预测的更强的M–O键，这表明当存在吸电子取代基时，如先前在M–C键强度中所见，M–O键稳定。另外，脂族醇的O–H活化产物在80°C时热不稳定，因为在1或2 d后观察到由β-消除形成的Tp'Rh（PMe 3）H 2重排。苯甲醇和2

  DOI：

  10.1021/acs.inorgchem.6b01992

文献信息

• Substitution and Hydrogenation Reactions on Rhodium(I)−Ethylene Complexes of the Hydrotris(pyrazolyl)borate Ligands Tp‘ (Tp‘ = Tp, Tp^Me2)
  作者：M. Carmen Nicasio、Margarita Paneque、Pedro J. Pérez、Antonio Pizzano、Manuel L. Poveda、Luis Rey、Sabine Sirol、Soraya Taboada、Marianela Trujillo、Angeles Monge、Caridad Ruiz、Ernesto Carmona

  DOI：10.1021/ic990419u

  日期：2000.1.1

  have been isolated by their reaction with O2. All the mononuclear Rh(I) complexes are formulated as 18e- trigonal bipyramidal species on the basis of IR and NMR spectroscopic studies. A series of dihydride complexes of Rh(III) of formulation Tp'RhH2(PR3) have been prepared by the hydrogenation of the corresponding ethylene derivatives. Complexes [TpRh]2(mu-CNCy)3, TpMe2Rh(C2H4)(PEt3), and TpMe2Rh(O2)(PEt3)

  从[RhCl（C2H4）2] 2获得了双（乙烯）Rh物种TpMe2Rh（ ）2（1 *）（TpMe2 =三（3,5-二甲基-1-吡唑-1-基）氢硼酸盐）。 KTpMe2。配合物1 *在溶液中易分解，主要生成丁二烯物种TpMe2Rh（eta74-C4H6）。在固态下，其热分解遵循不同的过程，烯丙基TpMe2RhH（syn-C3H4Me）作为外向异构体和内向异构体的混合物清晰地获得。配合物Tp'Rh（ ）2（Tp'= Tp，TpMe2）与PR3反应后可得到单取代物质Tp'Rh（ ）（PR3），但与L = CO或CNR反应不同：Tp化合物产生双核[ TpRh] 2（mu-L）3配合物，而在1 *的情况下，获得TpMe2Rh（ ）（L）物种。配合物TpMe2Rh（ ）（PR3）的乙烯配体不稳定，并通过与O2反应分离了组成为TpMe2Rh（O2）（PR3）的几种过氧化合
• Synthesis, structure, and reductive elimination in the series Tp′Rh(PR3)(ArF)H; Determination of rhodium–carbon bond energies of fluoroaryl substituents
  作者：Taro Tanabe、William W. Brennessel、Eric Clot、Odile Eisenstein、William D. Jones

  DOI：10.1039/c0dt00157k

  日期：——

  solutions at 140 °C were investigated, but were complicated by the formation of the rhodium(I) bisphosphine complex, Tp′Rh(PMe3)2 (4). On the other hand, thermal reactions of (9) in THF-d8 solutions at 120 °C resulted in the formation of an intramolecular C–H bond activated complex of the phenyl group on the phosphorus atom, Tp′Rh(κ2-C6H4-2-PMe2)H (7), which prevents the formation of the corresponding

  Tp'Rh（PR 3）（Ar F）H类型的一系列配合物，其中PR 3 =PMe 3（3）及PMe 2 Ph（9），AR ˚F= C 6 F 5（a），2,3,4,5-C 6 F 4 H（b），2,3,5,6-C 6 F 4 H（c），2,4,6-C 6 F 3 H 2（d），2,3-C 6 F 2 H 3（e），2,5-C 6 F 2 H 3（g）和2-C 6 FH 4（h）和Tp′ = 三（3,5-二甲基吡唑基）硼酸酯通过[Tp'Rh（PR 3）]片段与相应的氟化芳烃的反应合成了稳定的结晶化合物，并通过NMR光谱和元素分析以及X射线晶体学对其结构进行了表征。从配合物3a-h中还原消除氟芳烃的动力学。苯-d 6 对140°C的溶液进行了研究，但由于形成了 铑（I）双膦 复杂的， Tp′Rh（PMe 3）2（4）。另一方面，（9）的热反应在四氢呋喃-d 8在120℃下的解决方案导致分子内C-
• C−H Activation Reactions on Rh(I)−Ethylene Complexes of the Hydrotris(3,5-dimethylpyrazolyl)borate Ligand, Tp^Me_²
  作者：Margarita Paneque、Pedro J. Pérez、Antonio Pizzano、Manuel L. Poveda、Soraya Taboada、Marianela Trujillo、Ernesto Carmona

  DOI：10.1021/om990376p

  日期：1999.10.1

  TpMe2Rh(C2H4)(PR3) (R = Me, Et) are also efficient reagents for the C−H bond activation of C6H6, py, or thiophene. In the latter case, rupture of the C−S bond is also detected, although the C−S bond activation complexes are thermodynamically disfavored with respect to those derived from the cleavage of one of the α-C−H bonds.

  N供体路易斯碱（例如乙腈或吡啶）与Rh（I）化合物Tp Me 2 Rh（C 2 H 4）2（1）反应，得到Rh（III）衍生物Tp Me 2 Rh（CH CH 2）（ c ^ 2 ^ h 5）（L）（2，3）作为反应的动力学产品。在60℃加热后，乙腈加合物2转化为Tp Me 2 Rh（C 2 H 4）（NCMe）（5）。在类似条件下，2如同位素标记研究所示，它能够在涉及1的中间过程中诱导C 6 H 6的C H键之一的活化。膦加合物Tp Me 2 Rh（C 2 H 4）（PR 3）（R = Me，Et）也是激活C 6 H 6，py或噻吩的CH键的有效试剂。在后一种情况下，尽管相对于由α-CH键之一的裂解所衍生的那些键，CS键活化复合物在热力学上是不利的，但也检测到了CS键的断裂。
• Oxidative Addition of Chlorohydrocarbons to a Rhodium Tris(pyrazolyl)borate Complex
  作者：Yunzhe Jiao、William W. Brennessel、William D. Jones

  DOI：10.1021/acs.organomet.5b00131

  日期：2015.4.27

  The reactive fragment [Tp'Rh(PMe3)], generated from the thermal precursor Tp'Rh(PMe3)(Me)H, is found to cleave the CCl bonds of chlorohydrocarbons under mild conditions. Reaction with chloromethane gives clean formation of an initial CH activation product, which rearranges to form the CCl activation product at 30 degrees C. Reaction with dichloromethane or benzyl chloride gives a mixture of CCl activation products as well as products from chlorination. Reaction with chlorocyclohexane gives a mixture of intermediates from CH activation, which react further upon heating to give a CCl cleavage product as well as the beta-chloride elimination product Tp'Rh(PMe3)(Cl)H plus cyclohexene. Complete conversion from a CH activation product to a CCl activation product was observed in the reaction with 1,2-dichloroethylene, where beta-elimination is circumvented. Activation of 1-chlorobutane, 1,2-dichloroethane, or 1,4-dichlorobutane gives a mixture of CCl activation products as well as Tp'Rh(PMe3)(Cl)H plus olefin. Similar to the case for activation of methylene chloride, CCl activation and hydride/chloride exchange was observed in the reaction with benzyl chloride, where CH activation was not seen. The reaction with chlorobenzene gives isomeric species resulting from CH activation, which react further to give the corresponding chloride derivatives upon heating. Reaction with pentachlorobenzene gives a cyclometalated product from CH bond cleavage in the phosphine ligand. These reactions are compared and contrasted with related photoreactions with the [Tp'Rh(CNneopentyl)] analogue, where CH activation is solely observed in most cases. Mechanistic studies suggest the spectator ligand dependent reactivity relies greatly on the dissociation energy of the Tp'RhL bond.
• Synthesis, characterization, and C–H/C–C cleavage reactions of two rhodium–trispyrazolylborate dihydrides
  作者：Douglas D. Wick、William D. Jones

  DOI：10.1016/j.ica.2009.03.022

  日期：2009.9

  Treatment of Tp'Rh(PMe3)Cl-2 and Tp'Rh(CNCH2CMe3)Cl-2 with Cp2ZrH2 produces Tp'Rh(PMe3)H-2 and Tp'Rh(CNCH2CMe3) H-2, respectively, in excellent yield. Photolysis of benzene solutions of each dihydride complex generates hydrogen and the fragment [Tp'Rh(L)] which inserts into the solvent C-H bond. The phosphine dihydride has also been shown to be a catalyst for the hydrogenation of biphenylene, showing a capability to cleave C-C bonds. Reductive elimination of benzene from Tp'Rh(PMe3)PhH is nearly 250 times slower than from Cp*Rh(PMe3)PhH. (C) 2009 Elsevier B.V. All rights reserved.