di-m-chloro-bis{2-(di-ortho-tolylphosphino)benzyl-C,P}dipalladium(II) | 199609-05-7

• 英文名称: di-m-chloro-bis{2-(di-ortho-tolylphosphino)benzyl-C,P}dipalladium(II)
• 英文别名: [Pd(μ-Cl)(o-CH2C6H4P(o-tolyl)2)-(C,P)]2；[Pd(μ-Cl)(o-CH2C6H4P(o-tol)2)]2；[Pd(μ-Cl)(CH2C6H4-o-P(o-tolyl)2)]2；[Pd(μ-Cl)(CH2C6H4P(o-tolyl)2-C,P)]2
• CAS: 199609-05-7
• 化学式: C₄₂H₄₀Cl₂P₂Pd₂
• 分子量: 890.473
• InChiKey: BGFSEYIERRTIDF-UHFFFAOYSA-L

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：

  di-m-chloro-bis{2-(di-ortho-tolylphosphino)benzyl-C,P}dipalladium(II) 在 AgClO₄ 、 THF 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 为溶剂， 生成 [Pd(CH2-C6H4-P(o-tolyl)2-κC,P)(dimethyldithiocarbamate)HgI(μ-I)]2
  参考文献：
  名称：

  Reactivity of [M(C∧P)(S₂C-R)] (M = Pd, Pt; C∧P = CH₂-C₆H₄-P(o-tolyl)₂-κC,P; R = NMe₂, OEt) toward HgX₂ (X = Br, I). X-ray Crystal Structures of [Pt{CH₂-C₆H₄P(o-tolyl)₂-κC,P}(S₂CNMe₂)HgI(μ-I)]₂ and [PdBr(S₂COEt){μ-P(o-tolyl)₂-C₆H₄-CH₂-}HgBr]·0.5HgBr₂·C₂H₄Cl₂

  摘要：

  The reaction of the complexes [Pt(C boolean AND P)(S2C-R)] (C boolean AND P = CH2-C6H4-P(o-tolyl)(2)-kappa C,P,R = NMe2, OEt) with an equimolar amount of HgX2 (X = Cl, Br) gives the tetranuclear derivatives [Pt(C boolean AND P)(S2C-R)HgX(mu-X)](2) [R = NMe2, X = Br (3), I (4); R = OEt, X = Br (5), I (6)] containing Pt-->Hg donor-acceptor bonds. The reaction of [Pd(C boolean AND P)(S2CNMe2)] with HgI2 affords the complex [Pd(C boolean AND P)(S2CNMe2)HgI(mu-I)](2) (9) similar to the complexes 3-6; by contrast the reaction of [Pd(C boolean AND P)(S2C-R)] (R = NMe2, OEt2) with HgBr2 leads to the corresponding dinuclear complexes [PdBr(S2C-R)(mu-C boolean AND P)HgBr] [R = NMe2 (10), OEt (11)] with the didentate C boolean AND P cyclometalating ligand, -CH2-C6H4-P(o-tolyl)(2)-C,P (resulting from the C-H activation of the P(o-tolyl)(3)) acting in an unprecedented bridging mode. Compound 4 (C24H26HgI2NPPtS2) crystallizes in the triclinic system, space group P (1) over bar: a = 9.5755(11) Angstrom, b = 11.1754(12) Angstrom, c = 14.501(2) Angstrom, alpha = 84.826(5)degrees, beta = 81.611(7)degrees, gamma = 68.606(9)degrees, V = 1428.5(3) Angstrom(3), and Z = 1. Compound 11.0.5 HgBr2 . C2H4Cl2 (C24H25Br2HgOPPdS2 . 0.5 HgBr2 . C2H4Cl2) crystallizes in the monoclinic system, space group P2(1)/c: a 15.571(2) Angstrom, b = 10.7425(10) Angstrom, c = 19.655(2) Angstrom, beta = 94.741(12)degrees, V = 3276.5(5) Angstrom(3), and Z = 4.

  DOI：

  10.1021/ic970584e
• 作为产物：
  描述：

  三(邻甲基苯基)磷 以 甲醇 、 二氯甲烷 、 丙酮 为溶剂， 生成 di-m-chloro-bis{2-(di-ortho-tolylphosphino)benzyl-C,P}dipalladium(II)
  参考文献：
  名称：

  Reactivity of [M(C∧P)(S₂C-R)] (M = Pd, Pt; C∧P = CH₂-C₆H₄-P(o-tolyl)₂-κC,P; R = NMe₂, OEt) toward HgX₂ (X = Br, I). X-ray Crystal Structures of [Pt{CH₂-C₆H₄P(o-tolyl)₂-κC,P}(S₂CNMe₂)HgI(μ-I)]₂ and [PdBr(S₂COEt){μ-P(o-tolyl)₂-C₆H₄-CH₂-}HgBr]·0.5HgBr₂·C₂H₄Cl₂

  摘要：

  The reaction of the complexes [Pt(C boolean AND P)(S2C-R)] (C boolean AND P = CH2-C6H4-P(o-tolyl)(2)-kappa C,P,R = NMe2, OEt) with an equimolar amount of HgX2 (X = Cl, Br) gives the tetranuclear derivatives [Pt(C boolean AND P)(S2C-R)HgX(mu-X)](2) [R = NMe2, X = Br (3), I (4); R = OEt, X = Br (5), I (6)] containing Pt-->Hg donor-acceptor bonds. The reaction of [Pd(C boolean AND P)(S2CNMe2)] with HgI2 affords the complex [Pd(C boolean AND P)(S2CNMe2)HgI(mu-I)](2) (9) similar to the complexes 3-6; by contrast the reaction of [Pd(C boolean AND P)(S2C-R)] (R = NMe2, OEt2) with HgBr2 leads to the corresponding dinuclear complexes [PdBr(S2C-R)(mu-C boolean AND P)HgBr] [R = NMe2 (10), OEt (11)] with the didentate C boolean AND P cyclometalating ligand, -CH2-C6H4-P(o-tolyl)(2)-C,P (resulting from the C-H activation of the P(o-tolyl)(3)) acting in an unprecedented bridging mode. Compound 4 (C24H26HgI2NPPtS2) crystallizes in the triclinic system, space group P (1) over bar: a = 9.5755(11) Angstrom, b = 11.1754(12) Angstrom, c = 14.501(2) Angstrom, alpha = 84.826(5)degrees, beta = 81.611(7)degrees, gamma = 68.606(9)degrees, V = 1428.5(3) Angstrom(3), and Z = 1. Compound 11.0.5 HgBr2 . C2H4Cl2 (C24H25Br2HgOPPdS2 . 0.5 HgBr2 . C2H4Cl2) crystallizes in the monoclinic system, space group P2(1)/c: a 15.571(2) Angstrom, b = 10.7425(10) Angstrom, c = 19.655(2) Angstrom, beta = 94.741(12)degrees, V = 3276.5(5) Angstrom(3), and Z = 4.

  DOI：

  10.1021/ic970584e

文献信息

• Different Coordination Modes of the Polyfunctional Ylide Ph ₃ P=C(H)C(O)CH ₂ C(O)OEt: <i>C‐</i> vs. <i>O</i> , <i>O′</i> ‐Bonding in Pd ^II , Pt ^II and Au ^I Complexes
  作者：Marta Carbó、Larry R. Falvello、Rafael Navarro、Tatiana Soler、Esteban P. Urriolabeitia

  DOI：10.1002/ejic.200300801

  日期：2004.6

  the ylidic carbon, which is transformed into a phosphonium group generating the zwitterion [Ph3PCH2C(O)=C(H)−C(=O)OEt], which coordinates to the metal center as an O,O′-chelating ligand. Treatment of 1 with [AuCl(SC4H8)] or [Au(PPh3)(OCMe2)]ClO4 gave [AuClC(H)(PPh3)C(O)CH2COOEt}] (10) or [AuC(H)(PPh3)C(O)CH2COOEt}(PPh3)]ClO4 (11), in which the ylide is C-bonded. The X-ray crystal structures of complexes

  已确定配合物 2a、9 和 10 的 X 射线晶体结构。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
• Reactivity of dimeric cyclopalladated complexes with an (sp)C–Pd bond toward KPPh2
  作者：Gerard C. Dickmu、Nicholas J. Korte、Irina P. Smoliakova

  DOI：10.1016/j.jorganchem.2015.07.023

  日期：2015.11

  Reactions of KPPh2 with dimeric C,N, C,P and C,S cyclopalladated complexes (CPCs) 1a−g containing an (sp3)C–Pd bond were investigated. The CPCs used in the study were obtained from D-camphor O-methyloxime (a), l-fenchone O-methyloxime (b), 4,4-dimethyl-2-phenyl-2-oxazoline (c), 8-methylquinoline (d), trimesitylphosphine (e), tri(O-tolyl)phosphine (f) and 2,6-dimethylthioanisole (g). The dichloro-bridged

  研究了KPPh 2与二聚C，N，C，P和C，S含（sp 3）C – Pd键的环钯配合物（CPC）1a - g的反应。研究中使用的CPC是从D-樟脑O-甲基肟（a），l- fenchone O-甲基肟（b），4,4-二甲基-2-苯基-2-恶唑啉（c），8-甲基喹啉（c）获得的d），三苯甲基膦（e），三（邻甲苯基）膦（f）和2,6-二甲基硫代苯甲醚（g）。二氯桥联的CPCs 1a，b，d，f，g和双乙酰桥联的类似物μ -OAc-1d与4.5当量反应。在室温下，在THF中浓缩KPPh 2 ，以20-51％的产率得到膦2a，b或氧化膦8d，f，g。配合物1a，b，d与1当量反应。KPPh 2的产率为33-56％，产生相应的μ-氯-μ-二苯基磷基CPCs 3a，b，d。在CPC 1c与4.5当量的反应中。KPPh 2，带有两个PPh的复合物4c分离出2个桥接配体，收率为36％。通过1 H，13 C
• Stabilized Bis-ylides as a Source of Carbene Ligands in Palladium(II) and Platinum(II) Complexes
  作者：Larry R. Falvello、Rosa Llusar、Marina E. Margalejo、Rafael Navarro、Esteban P. Urriolabeitia

  DOI：10.1021/om020467d

  日期：2003.3.1

  2Me)}(L)(PPh3)](ClO4) (L = SC4H8, 9; PPh3, 10), probably through the initial formation of an ylide-carbene complexsimilar to 1−6followed by the migratory insertion of the carbene ligand into the Pd−C(C6F5) bond and coordination of the newly generated ylide function. The crystal structure of complex 1a·CH2Cl2 has been analyzed by X-ray diffraction.

  α稳定的双内酯[Ph 3 P C（CO 2 Me）-C（CO 2 Me）PPh 3 ]与M（II）双溶剂化物衍生物顺式[[M（C 6 F 5）] 2（OC 4 H 8）2 ]或[M（C∧X）（OC 4 H 8）2 ] ClO 4（M = Pd，PT;C∧X=正金属配体），生成ylide-carbene配合物顺式- [M（C 6 F 5）2 C（CO 2 Me）−C（CO 2 Me）（PPh3）}（PPh 3）]（M = PT 1a，Pd 1b）或[M（C∧X）C（CO 2 Me）-C（CO 2 Me）（PPh 3）}（PPh 3）] ClO 4（M = PT，C∧X= ö -CH 2 C ^ 6 ħ 4 P（ø甲苯基）2，2 ; M =钯，C∧X= ö -CH 2 C ^ 6 ħ 4 P（ø甲苯基）2，3 ; CH 2 C ^ 9 ħ 6 N-C 8，N，4 ; NC 5 H ^ 4 -
• The use of control experiments as the sole route to correct the mechanistic interpretation of mercury poisoning test results: The case of P,C-palladacycle-catalysed reactions
  作者：Olga N. Gorunova、Ivan M. Novitskiy、Yuri K. Grishin、Igor P. Gloriozov、V.A. Roznyatovsky、Victor N. Khrustalev、Konstantin A. Kochetkov、Valery V. Dunina

  DOI：10.1016/j.jorganchem.2020.121245

  日期：2020.6

  even at a higher temperature and with a greater excess of Hg(0). The structures of these mercurials have been convincingly confirmed spectrally (1Н, 13С, 31Р and 199Hg NMR), and via X-ray diffraction study and DFT calculations for the chloride mercurial. Our results and the analysis of known data on the mercury diagnostics of catalytic systems with classical and anomalous P,C-precatalysts enable us to

  在金属汞相互作用与三-环钯衍生物的研究邻-tolylphosphine [（κ 2 P，C -L）的Pd（μ-X）} 2 ]，由与地层金属汞钯环的氧化还原金属转移的P，C -chelated benzylmercurials [（κ 2 P，C -L）HGX]显露在过量汞（0）的存在下适度的温度。相反，即使在较高的温度下和过量的HG（0）下，使用相同的氯化物P，C-预催化剂对Suzuki反应进行的汞（0）测试也给出了负面结果。这些汞的结构已经令人信服地证实光谱（1 Н，13 С，31 Р和199汞柱NMR），并通过用于氯乙烯水银X射线衍射研究和DFT计算。我们的研究结果和对与经典和反常催化体系的汞诊断已知数据的分析P，C -precatalysts使我们能够假定钯环的完整状态存在于关键阴离子中间体[（κ 2 P，C -L ）Pd 0 ] – Suzuki和Heck反应的催化循环，与钯（I
• Cyclometallated Pt(ii) and Pd(ii) complexes with a trithiacrown ligand
  作者：Daron E. Janzen、Donald G. VanDerveer、Larry F. Mehne、Demétrio A. da Silva Filho、Jean-Luc Brédas、Gregory J. Grant

  DOI：10.1039/b717910c

  日期：——

  one-electron metal-centered oxidations for all Pt(II) complexes, but unusual two-electron reversible oxidations for the Pd(II) complexes of ppy and bzq. The X-ray crystal structures of each complex indicate an axial M–S interaction formed by the endodentate conformation of the [9]aneS3 ligand. The structure of [Pd(bzq)([9]aneS3)](PF6) exhibits disorder in the [9]aneS3 conformation indicating a rare exodentate

  我们报告的合成和表征的一系列环金属化的铂（Ⅱ）和钯（Ⅱ）结合通量trithiacrown配体 1,4,7-三硫代环壬烷（[9] aneS 3）。[M（C ^ N）（µ-Cl）] 2（M = Pt（II），Pd（II）; C; N = 2-苯基吡啶酸酯（ppy）或7,8-苯并喹啉酸酯（z）），然后加入[9] aneS 3复分解用NH 4 PF 6制得[M（C⁁N）（[9] aneS 3）]（PF 6）。配合物[M（C⁁P）（[9] aneS 3）]（PF 6）（M = Pt（II），Pd（II）; C = P = CH 2 C 6 H 4 P（o-甲苯基） ）2 - C，P } -）由它们各自的[Pt（C⁁P）（µ-Cl）] 2或[Pd（C⁁P）（µ-O 2 CCH 3）] 2（C⁁P ）起始材料。所有五个新的复合物都具有多核的完整特征核磁共振， 红外 和 紫外可见 光谱学 元素分析， 循