chloro(dimethyldithiocarbamato)(triethylphosphine)palladium(II) | 132912-15-3

• 分子结构分类: 有机化合物 - 有机硫化合物
• 英文名称: chloro(dimethyldithiocarbamato)(triethylphosphine)palladium(II)
• CAS: 132912-15-3
• 化学式: C₉H₂₁ClNPPdS₂
• 分子量: 380.251
• InChiKey: QMWHORPOKPOOIE-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  4.25
• 重原子数：
  15.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  3.24
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  chloro(dimethyldithiocarbamato)(triethylphosphine)palladium(II) 以 四氢呋喃 、 甲苯 为溶剂， 生成
  参考文献：
  名称：

  （Me2NCS2）Pd（PR3）（烷基）配合物中烷基配体的异构化。烷基中杂原子取代基对烷基异构化平衡和烷基金属配合物稳定性的影响

  摘要：

  A series of complexes of unusually stable alkylpalladium complexes of the formula (Me2NCS2)Pd(PR3) (alkyl) (R = Me, Et) have been prepared from the reaction of (Me2NCS2)Pd(PR3)CI and the appropriate alkyllithium or Grignard reagent. The substituted complexes Me2NCS2)Pd(PEt3)(CH2CH2CF3) and (Me2NCS2)Pd(PEt3)(CH2CH2CN) were prepared in similar reactions, and the isomer of the latter, (Me2NCS2)Pd(PEt3)(CH(CN)CH3), was prepared from the low-temperature, in situ reaction of (Me2NCS2)Pd(PEt3)H and CH2CHCN. The reaction of (Me2NCS2)Pd(PEt3)Cl with Li[C(CH3)3]CuCN gives a color change indicative of the formation of the alkylpalladium complex, but this tert-butyl compound decomposes above -40-degrees-C with the formation of its isomer, (Me2NCS2)Pd(PEt3)(CH2CH(CH3)2). With this one exception, all of these complexes are extremely stable, especially the substituted alkyl complexes, which can be heated over 100-degrees-C in solution for extended periods without noticeable decomposition. Heating the unsubstituted isomers at 75-degrees-C in solution leads to isomerization of the alkyl ligand. For example, heating either (Me2NCS2)Pd(PEt3)(CH2CH2CH3) or (Me2NCS2)Pd(PEt3)(CH(CH3)2) leads to a 10:1.0 equilibrium mixture, respectively, of the two. An equilibrium mixture of 10:1.0 is found for the other alkyl ligands studied. This 1.6 kcal/mol difference between the isomers is proposed to be the difference in energy between secondary versus primary alkylmetal complexes in the absence of steric constraints imposed by other ligands in the coordination sphere. At 120-degrees-C, the primary isomer (Me2NCS2)Pd(PEt3)(CH2CH2CN) isomerizes completely to the secondary isomer (Me2NCS2)Pd(PEt3)(CH(CN)CH3), whereas (Me2NCS2)Pd(PEt3) (CH2CH2CF3) isomerizes to a 1:1 mixture with its secondary isomer. The alkyl ligand in (Me2NCS2)Pd(PEt3)(CH(CH3)2) exchanges with 1-hexene to yield an isomeric mixture of all three (Me2NCS2)Pd(PEt3)(hexyl) isomers. This reaction is only successful for monosubstituted alkenes. Kinetic studies of the alkyl isomerization reaction show that it is first order and that Lewis bases, especially added PEt3, substantially slow the reaction. It has also been shown that the free and complexed PEt3 exchange rapidly. The structure of ((CH2)4NCS2)Pd(PEt3)(CH(CN)CH3) has been determined by X-ray crystallography. Crystal data: triclinic, P1BAR, a = 11.865 (3) angstrom, b = 16.003 (5) angstrom, c = 10.060 (3) angstrom, alpha = 93.45 (3)-degrees, beta = 91.27 (3)-degrees, gamma = 101.08 (3)-degrees, V = 1870 angstrom3, Z = 4, R(F) = 4.1 %, and R(wF) = 5.8%. There are no obvious structural features in the standard square planar geometry of this compound that indicate why the cyanide substituent stabilizes this branched isomer in favor of the linear isomer.

  DOI：

  10.1021/om00060a054

文献信息

• Alkene and alkyne insertion reactions with the unstable palladium hydride complex (Me2NCS2)Pd(PEt3)H and carbon monoxide insertion reactions with (Me2NCS2)Pd(PEt3)(alkyl) complexes
  作者：Daniel L. Reger、David G. Garza

  DOI：10.1021/om00026a043

  日期：1993.2

  The unstable complex (Me2NCS2)Pd(PEt3)H is prepared in situ at low temperature by the reaction of (Me2NCS2)Pd(PEt3)Cl and LiHBEt3. The reaction of (Me2NCS2)Pd(PEt3)H with CH2=CHCN at low temperature gives (Me2NCS2)Pd(PEt3)(CH(CN)CH3). The hydride reacts with CH3O2CC=CCO2CH3 to produce both the Z and E isomers of (Me2NCS2)Pd(PEt3)-[(CH3O2C)C=C(CO2CH3)H] in a 4:1 ratio. A similar reaction with the unsymmetrical alkyne CH3O2CC=CCH3 yields all four possible insertion products. The insertion reaction with HC=CCH2CH2CH3 yields (Me2NCS2)Pd(PEt3)[(CH3CH2CH2)C=CH2] and (Me2NCS2)-Pd(PEt3)[(E)-(H)C=C(H)CH2CH2CH3] in a 4:1 ratio. The complexes (Me2NCS2)Pd(PEt3)R (R = methyl, n-propyl, isopropyl) react with carbon monoxide to yield the respective acyl complexes, (Me2NCS2)Pd(PEt3)COR. The isopropyl acyl complex will not decarbonylate or isomerize to the n-propyl derivative when heated in solution at 75-degrees-C. (Me2NCS2)Pd(PEt3)COCH3 reacts with CH3O2CC=CCO2CH3 to yield (Me2NCS2)Pd(PEt3)[(CH3O2C)C=C(COCH3)CO2CH3].
• Reger, Daniel L.; Garza, David G.; Lebioda, Lukasz, Organometallics, 1991, vol. 10, # 4, p. 902 - 906
  作者：Reger, Daniel L.、Garza, David G.、Lebioda, Lukasz

  DOI：——

  日期：——
• Reger, Daniel L.; Collins, James E., Inorganic Chemistry, 1995, vol. 34, # 9, p. 2473 - 2475
  作者：Reger, Daniel L.、Collins, James E.

  DOI：——

  日期：——
• Syntheses of carbene and alkenyl derivatives of palladium. Solid-state structures of {(Me2NCS2) Pd(PEt3) [η1−C(N(CH3) C(CH3)3) CH3]}BPh4 and {(Me2NCS2)Pd(PEt3)[η1−C(NHC(CH3)3)CH3]}PF6 · Et2O
  作者：Daniel L. Reger、James E. Collins

  DOI：10.1016/0022-328x(94)05248-a

  日期：1995.4

  The reaction of (t)BuNC and (Me(2)NCS(2))Pd(PEt(3))CH3 yields (Me(2)NCS(2))Pd(PEt(3))[eta(1)-C(NC(CH3)(3)CH3]. Reaction of this amino acyl complex with [(CH3)(3))]BF4 yields, after anion exchange, Me(2)NCS(2))Pd(PEt(3))[eta(1)-C(NHC(CH3)(3)CH3]}BPh(4). An analogous reaction with NH4PF6 yields (Me(2)NCS(2))Pd(PEt(3))[eta(1)-C(NHC(CH3)(3)CH3]}PF6. Both of these carbene complexes have been characterized crystallographically. Crystal data: (Me(2)NCS(2))Pd(PEt(3))[eta(1)-C(N(CH3)C(CH3)(3))CH3]}BPh(4) triclinic, P (1) over bar, a = 12.253(12) Angstrom, b = 14.422(5) Angstrom, c = 11.564(5) Angstrom, alpha = 97.83(3)degrees, beta = 93.04(6)degrees, gamma = 85.21(5)degrees, V = 2018 Angstrom(3), Z = 2, T = 298 K, R(F) = 7.6%; (Me(2)NCS(2))Pd(PEt(3))[eta(1)-C(NHC(CH3)(3))CH3]}PF6 . Et(2)O triclinic, P (1) over bar, a = 12.844(2) Angstrom, b = 15.247(2) Angstrom, c = 8.312(2) Angstrom, alpha = 105.60(1)degrees, beta = 101.67(2)degrees, gamma = 90.20(1)degrees, V = 1533 Angstrom(3), Z = 2, T = 298 K, R(F) = 5.4%. In both complexes, the overall coordination geometry is approximately planar about both the palladium atom and carbene carbon atom, and these two planes are perpendicular. Reaction of (Me(2)NCS(2))Pd(PEt(3))[eta(1)-C(N(CH3)C(CH3)(3))CH3]}BPh(4) with LiCH3 results in deprotonation at the beta-carbon yielding (Me(2)NCS(2))Pd(PEt(3))[eta(1)-C(N(CH3)C(CH3)(3))-CH2], and this reaction is reversed with HBF4 . Et(2)O. The reaction of LiC(OCH2CH3)=CH2 with (Me(2)NCS(2))Pd(PEt(3))Cl yields (Me(2)NCS(2))Pd(PEt(3))[eta(1)-C(OCH2CH3)=CH2]. This alkenyl complex reacts with BH3 in ethanol to yield (Me(2)NCS(2))Pd(PEt(3))[eta(1)-CH(OCH2CH3)CH3]. (Me(2)NCS(2))Pd(PEt(3))[eta(1)-C(OCH2CH3)=CH2] also forms in the reaction of (Me(2)NCS(2))Pd(PEt(3))H and HC=COCH2CH3, along with both geometric isomers of (Me(2)NCS(2))Pd(PEt(3))[eta(1)-CH=CH(OCH2CH3)]. Reaction of phenylacetylene and (Me(2)NCS(2))Pd(PEt(3))H yields mainly (Me(2)NCS(2))Pd(PEt(3))eta(1)-C(Ph)=CH2) with small amounts of one of the other regioisomers present.