[(DTBPX)PdCl₂] | 428863-70-1

• 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: [(DTBPX)PdCl₂]
• 英文别名: [(bis(di-tert-butyl)phosphino-o-xylene)PdCl₂]；[(tbpx)PdCl2]；[Pd((1,2-CH2PBu2(t))2C6H4))Cl2]；[Pd(d(t)bpx)Cl2]；[(1,2-(CH2P(t-Bu)2)2C6H4)PdCl2]；ditert-butyl-[[2-(ditert-butylphosphanylmethyl)phenyl]methyl]phosphane;palladium(2+);dichloride
• CAS: 428863-70-1
• 化学式: C₂₄H₄₄Cl₂P₂Pd
• 分子量: 571.887
• InChiKey: IZJNVBRUDIJSOF-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  2.85
• 重原子数：
  29
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [(DTBPX)PdCl₂] 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  Characterization and Dynamics of [Pd(L−L)H(solv)]⁺, [Pd(L−L)(CH₂CH₃)]⁺, and [Pd(L−L)(C(O)Et)(THF)]⁺ (L−L = 1,2-(CH₂PBu^t₂)₂C₆H₄):  Key Intermediates in the Catalytic Methoxycarbonylation of Ethene to Methylpropanoate

  摘要：

  A detailed spectroscopic study has allowed the solution structure and dynamic properties of all the intermediates in the Pd-catalyzed methoxycarbonylation of ethene to be established. [Pd(L-L)H(solv)](-) 1 (L-L = 1,2-(CH2PBu2t)(2)C6H4; solv = MeOH, 1a; (PrOH)-O-n, 1b; THF, 1c; EtCN, 1d) is static, and the two inequivalent P atoms do not become equivalent through solvent exchange over all the temperatures studied. [Pd(L-L)(CH2CH3)](+), 2, contains a strong beta-agostic C-H interaction which is remarkably stable and is not displaced even in strongly coordinating solvents such as EtCN. C-alpha and C-beta Of the ethyl group in 2 become equivalent via a stereospecific interchange involving [Pd(L-L)H(eta(2)-C2H4)](+) without making the two P atoms equivalent; at higher temperatures these two inequivalent P atoms do become equivalent probably via a T-shaped intermediate. For [Pd(L-L)(C(O)Et)(solv)](+), 6, there is no beta-agostic C-H interaction and multiple C-13-labeling of the C(O)Et group shows that the inequivalent P atoms become equivalent via movement of the intact C(O)Et group. The crystal structure of the related complex [Pd(L-L)(C(O)Et)Cl] cocrystallized with dibenzylacetone has been determined.

  DOI：

  10.1021/om010938g
• 作为产物：
  描述：

  Pd(DBPMB)(DBA) 、 丙酰氯 以 乙醚 为溶剂， 以90%的产率得到[(DTBPX)PdCl₂]
  参考文献：
  名称：

  Characterization and Dynamics of [Pd(L−L)H(solv)]⁺, [Pd(L−L)(CH₂CH₃)]⁺, and [Pd(L−L)(C(O)Et)(THF)]⁺ (L−L = 1,2-(CH₂PBu^t₂)₂C₆H₄):  Key Intermediates in the Catalytic Methoxycarbonylation of Ethene to Methylpropanoate

  摘要：

  A detailed spectroscopic study has allowed the solution structure and dynamic properties of all the intermediates in the Pd-catalyzed methoxycarbonylation of ethene to be established. [Pd(L-L)H(solv)](-) 1 (L-L = 1,2-(CH2PBu2t)(2)C6H4; solv = MeOH, 1a; (PrOH)-O-n, 1b; THF, 1c; EtCN, 1d) is static, and the two inequivalent P atoms do not become equivalent through solvent exchange over all the temperatures studied. [Pd(L-L)(CH2CH3)](+), 2, contains a strong beta-agostic C-H interaction which is remarkably stable and is not displaced even in strongly coordinating solvents such as EtCN. C-alpha and C-beta Of the ethyl group in 2 become equivalent via a stereospecific interchange involving [Pd(L-L)H(eta(2)-C2H4)](+) without making the two P atoms equivalent; at higher temperatures these two inequivalent P atoms do become equivalent probably via a T-shaped intermediate. For [Pd(L-L)(C(O)Et)(solv)](+), 6, there is no beta-agostic C-H interaction and multiple C-13-labeling of the C(O)Et group shows that the inequivalent P atoms become equivalent via movement of the intact C(O)Et group. The crystal structure of the related complex [Pd(L-L)(C(O)Et)Cl] cocrystallized with dibenzylacetone has been determined.

  DOI：

  10.1021/om010938g
• 作为试剂：
  描述：

  甲醇 、 一氧化碳 、 norbornene 在 [(DTBPX)PdCl₂] 、 三氟乙酸 作用下， 70.0 ℃ 、3.0 MPa 条件下， 反应 24.0h， 生成 methyl bicyclo<2.2.1>heptane-2-exo-carboxylate
  参考文献：
  名称：

  Room temperature asymmetric Pd-catalyzed methoxycarbonylation of norbornene: highly selective catalysis and HP-NMR studies

  摘要：

  合成了带有单齿和双齿膦配体（1-7）的钯配合物，并将其用作降冰片烯甲氧基羰基化反应的催化剂前体。含有配体 1、3 和 4 的催化体系具有优异的酯转化率（大于 99%）和选择性（大于 99%）。核磁共振研究表明，使用配合物 1a 作为前体，在催化条件下会形成质子化的膦 1-H+，因此该体系的活化不需要添加酸，因为在 CO 压力下，前体与甲醇反应会产生 2 个当量的 HCl，从而形成活性物质。此外，还观察到配体 4 在甲氧基羰基化条件下发生质子化，并分离和鉴定了二质子化的二膦。该化合物作为配体和酸源在催化反应中进行了测试，并提供了极佳的酯转化率和高选择性。

  DOI：

  10.1039/c2dt30267e

文献信息

• Transition Metal Cooperative Lewis Pairs Using Platinum(0) Diphosphine Monocarbonyl Complexes as Lewis bases
  作者：Krishna Mistry、Paul G. Pringle、Hazel A. Sparkes、Duncan F. Wass

  DOI：10.1021/acs.organomet.9b00568

  日期：2020.2.10

  The platinum(0)-diphosphine complex [Pt(CO)(L1)] (3, where L1 = 1,2-C6H4(CH2PtBu2)2) and its diphosphinite analogue [Pt(CO)(L2)] (11, where L2 = 1,2-C6H4(OPtBu2)2) act as Lewis bases in conjunction with the main group Lewis acid B(C6F5)3 to form frustrated or cooperative Lewis pairs. These systems activate dihydrogen, ethene/carbon monoxide, and phenylacetylene, leading to products that depend on the

  的铂（0）配合物-diphosphine [PT（CO）（L1）]（3，其中L1 = 1,2-C 6 H ^ 4（CH 2 P吨卜2）2）及其类似物diphosphinite [PT（CO） （L2）]（11，其中L2 = 1,2-C 6 H 4（OP t Bu 2）2）与主要基团路易斯酸B（C 6 F 5）3一起充当路易斯碱形成沮丧或合作的刘易斯对。这些系统激活二氢，乙烯/一氧化碳和苯乙炔，从而产生取决于所用确切配体的产物。这些对配体结构的细微变化会影响反应性，最显着的是在氢激活中，其中[[diphos] PT（μ-H）3 PT（diphos）] +或[（diphos）PT（μ-H） ）（μ-CO）PT（diphos）] +被观察到。用路易斯对对乙烯的活化导致先前报道的偶联产物，并且对该机理进行了探索。[PT（CO）（L）]的碱性通过苯乙炔的去质子化得到证明。使用类似钯络合物[Pd（CO
• Synthesis, X-ray characterisation and reactions of a trigonal planar palladium(0) carbonyl complex, (tbpx)PdCO
  作者：Ronan M. Bellabarba、Robert P. Tooze、Alexandra M. Z. Slawin

  DOI：10.1039/b305854a

  日期：——

  The novel complex (tbpx)PdCO (1), the first example of a structurally characterised sixteen electron, trigonal planar palladium(0) carbonyl complex, was prepared, characterised by NMR spectroscopy and X-ray crystallography, and some unusual aspects of its reactivity were studied.

  新型配合物 (tbpx)PdCO (1) 是第一个结构特征为 16 电子、三角平面钯 (0) 羰基配合物的实例，已制备完成，通过 NMR 光谱和 X 射线晶体学及其反应性的一些不寻常的方面进行了表征被研究了。
• Isomerizing Methoxycarbonylation of Alkenes to Esters Using a Bis(phosphorinone)xylene Palladium Catalyst
  作者：James D. Nobbs、Choon Heng Low、Ludger P. Stubbs、Cun Wang、Eite Drent、Martin van Meurs

  DOI：10.1021/acs.organomet.6b00813

  日期：2017.1.23

  The synthesis and characterization of bulky diphosphine 1,2-bis(4-phosphorinone)xylene, BPX, and its palladium complexes [(BPX)PdCl2] and [(BPX)Pd(O2CCF3)(2)] are described. BPX was evaluated as a ligand in Pd-catalyzed isomerizing methoxycarbonylation. A broad range of alkenes, including terminal, internal, branched, and functionalized alkenes, can be converted to esters with activities and selectivities matching or surpassing the performance of the state-of-the-art palladium bis(di(tert-butyl)phosphino-o-xylene (Pd-DTBPX) catalyst. A molecular structure of the precatalyst [(BPX)Pd(O2CCF3)2] was obtained showing a square planar geometry and a bite angle of 100.11(3)degrees. Rhodium carbonyl complexes [(BPX)Rh(CO)Cl] and [(DTBPX)Rh(CO)Cl] were synthesized to compare the relative electronic parameters, revealing a v(C 0) of 1956.8 and 1948.3 cm(-1), respectively, suggesting a reduced ability of BPX to donate electron density to the metal relative to DTBPX. Competitive protonation experiments between BPX and DTBPX in the presence of CH3SO3H exclusively produce [DTBPX(H)(2)](2+), providing additional evidence that BPX is a much weaker base than DTBPX. This could be due to either the effect of the electron-withdrawing ketone group in the phosphorinone ring or the compression of the C-P-C bond angle induced by the ring structure. The P-31 NMR (CDCl3) chemical shift of BPX is 5.6 ppm, upfield of DTBPX at 27.6 ppm. This anomalous result is attributed to a strong gamma substituent effect of C=0 in the BPX ligand. The improved activity of Pd-BPX, relative to Pd-DTBPX, could be attributed to a more electrophilic Pd-II center, which could accelerate the rate-determining methanolysis step.
• Clegg, William; Eastham, Graham R.; Elsegood, Mark R.J., Journal of the Chemical Society. Dalton Transactions (2001), 2002, # 17, p. 3300 - 3308
  作者：Clegg, William、Eastham, Graham R.、Elsegood, Mark R.J.、Heaton, Brian T.、Iggo, Jonathan A.、Tooze, Robert P.、Whyman, Robin、Zacchini, Stefano

  DOI：——

  日期：——