((i)Pr2PC2H4P(i)Pr2)Pd(C2H4) | 138234-21-6

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: ((i)Pr2PC2H4P(i)Pr2)Pd(C2H4)
• 英文别名: (d(i)ppe)Pd(ethene)；2-Di(propan-2-yl)phosphanylethyl-di(propan-2-yl)phosphane;ethene;palladium
• CAS: 138234-21-6
• 化学式: C₁₆H₃₆P₂Pd
• 分子量: 396.829
• InChiKey: SXWDGXJOKQELNJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.38
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  ((i)Pr2PC2H4P(i)Pr2)Pd(C2H4) 以 正戊烷 为溶剂， 生成
  参考文献：
  名称：

  (R₂PC₂H₄PR₂)Pd⁰−1-Alkyne Complexes

  摘要：

  Displacement of the ethene ligand in (d(i)ppe)Pd(C2H4)(d(i)ppe = (Pr2PC2H4PPr2)-Pr-i-Pr-i) by 1-alkynes RC = CH affords the mononuclear complexes (d(i)ppe)Pd(RC = CH) (R = Me (2a), Ph (3a), CO2 Me (4), SiMe3 (5)). The molecular structure of 3a has been determined by X-ray crystallography. Mononuclear 2a and 3a have been reacted with stoichiometric amounts of (d(i)ppe)Pd(eta(1).C3H5)(2) as a source for [(d(i)ppe)Pd-0] to yield the dinuclear derivatives {(d(i)ppe)Pd}(2)(mu.RC = CH)(R = Me (2b), Ph (3b)). By the reaction of (d(i)ppe)Pd(C2H4) with difunctional vinylacetylene the mononuclear complex (d(i)ppe)Pd{(1,2-eta(2))-RC = CH} (R = CH = CH2 (6a)) is formed, which is in equilibrium with isomeric (d(i)ppe)Pd{(3,4-eta(2))-H2C = CHC = CH} (6b). Addition of [(d(i)ppe)Pd-0] to 6a,b yields dinuclear {(d(i)ppe)Pd}(2)(mu-RC = CH) (R = CH = CH2 (6c)). Reaction of (d(i)ppe)Pd(C2H4) with butadiyne affords (d(i)ppe)Pd(eta(2)-HC = CC = CH (7c). From d(i)ppe, Pt(cod)(2), and C4H2 the Pt homologue has also been synthesized and thus, together with the already known Ni derivative, the series (d(i)ppe)M(eta(2)-HC = CC CH (M = Ni (7a), Pd (7c), Pt (7f)) is now complete. When 7c and [(d(i)ppe)Pd-0] are combined, the dinuclear complex {(d(i)ppe)Pd}(2)(mu-RC = CH (R = C = CH) (7e)) is formed in solution, whereas isomeric {(d(i)ppe)Pd}(2){mu-(1,2-eta(2)):(3,4-eta(2))-HC = CC = CH} (7d) is present in the solid state. The preparation of the Pd-0-1-alkyne complexes refutes the conventional wisdom that this type of compound is inherently unstable. By reaction of (d(i)ppe)Pd(C2H4) with internal alkynes C2R2 the complexes (d(i)ppe)Pd(RC = CR) (R = Me (8a), Ph (9), CO2Me (10), SiMe3 (11)) have also been prepared. Combining 8a with [(d(i)ppe)Pd-0] affords dinuclear {(d(i)ppe)Pd}(2)(mu-MeC = CMe)(8b). Finally, solution thermolysis of 2b and 8b gives rise to dinuclear alkyne-free Pd-2(d(i)ppe)(2) (12).

  DOI：

  10.1021/om9702035
• 作为产物：
  描述：

  、 乙烯 以 乙醚 为溶剂， 以62%的产率得到((i)Pr2PC2H4P(i)Pr2)Pd(C2H4)
  参考文献：
  名称：

  (R2PC2H4PR2)Pd0 alkene and ethyne complexes

  摘要：

  The palladium eta(3)-allyl complex Pd(eta(3)-C3H5)2 reacts with bidentate phosphanes iPr2PC2H4PiPr2 and tBu2PC2H4PtBu2 below -30-degrees-C to yield the light yellow, microcrystalline palladium(II) eta(1)-allyl compounds (R2PC2H4PR2)Pd(eta(1)-C3H5)2 (R = (i)Pr (1), (t)Bu (2)), which are stable to about -30-degrees-C. Above -30-degrees-C, the allyl substituents of 1 and 2 couple with reduction of palladium to form a mixture of (R2PC2H4PR2)Pd0 1,5-hexadiene complexes. When this reaction is carried out in 1,5-hexadiene, the complexes (R2PC2H4PR2)Pd(eta(2)-C6H10) (R = (i)Pr (3), (t)Bu (4)) are obtained in pure form. According to IR and NMR spectral data, the palladium atoms in 3 and 4 are coordinated at low temperature by the chelating diphosphane and (statically) by one of the two diene double bonds in a trigonal-planar geometry. At higher temperatures, a rapid exchange of the coordinated and uncoordinated double bonds occurs, passing through an intermediate with C2 symmetry. When suspensions of 1 in pentane and 2 in THF are warmed to 20-degrees-C, dinuclear diastereomers rac-/meso-{(R2PC2H4PR2)Pd}2(mu-eta(2):eta(2)-C6H10) (R = (i)Pr (5a,b), (t)Bu (6a,b)) are obtained, which upon treatment with 1,5-hexadiene furnish mononuclear derivatives 3 and 4. Similarly, when 1 is reacted with 1,5-cyclooctadiene at 20-degrees-C, the mono- and dinuclear interconvertible complexes ((i)Pr2PC2H4P(i)Pr2)Pd(eta(2)-C8H12) (7) and {((i)Pr2PC2H4P(i)Pr2)Pd}2(mu-eta(2):eta(2)-C8H12) (8) are produced. From the reaction of 1 and 2 with ethene, stable complexes (R2PC2H4PR2)Pd(C2H4) (R = (i)Pr (9), colorless; R = (t)Bu (10), tan) result. The colorless mononuclear palladium(0) ethyne complexes (R2PC2H4PR2)Pd(C2H2) (R = (i)Pr (11), (t)Bu (12)) may be prepared (a) by a displacement reaction of one of the isolated alkene complexes with ethyne, (b) by a reductive elimination and concomitant displacement reaction of the eta(1)-allyl complexes 1 and 2 with ethyne, or (c) in a one-pot synthesis from either Pd(eta(3)-C3H5)2 or Pd(eta(3)-2-MeC3H4)2 with (i)Pr2PC2H4P(i)Pr2 or (t)Bu2PC2H4P(t)Bu2, respectively, and ethyne in excess. When the mononuclear ethyne complexes 11 and 12 are combined with an equimolar amount of the corresponding eta(1)-allyl complex 1 or 2, or the alkene complexes (especially the mononuclear 1,5-hexadiene (3, 4) or ethene (9, 10) derivatives), yellow dinuclear palladium(0) complexes {(R2PC2H4PR2)Pd}2(mu-C2H2) (R = (i)Pr (13), (t)Bu (14)) are produced, in which the ethyne ligand bridges two palladium atoms. All the (diphosphane)palladium(0) alkene (3-10) and ethyne complexes (11-14) exhibit a trigonal-planar coordination geometry about the palladium atom. Most of the compounds have been isolated in high yield.

  DOI：

  10.1021/om00039a023

文献信息

• A palladium-catalysed stannole synthesis: development and mechanism
  作者：Jochen Krause、Christian Pluta、Klaus-R. Pörschke、Richard Goddard

  DOI：10.1039/c39930001254

  日期：——

  A palladium-catalysed stannole synthesis is described and its mechanism elucidated by the synthesis of several conceivable intermediates, which have been fully characterized (NMR, X-ray structure analyses).

  该论文描述了一种钯催化的司坦唑合成方法，并通过合成几种可想象的中间产物阐明了其机理，这些中间产物已被完全表征（核磁共振、X 射线结构分析）。
• Synthesis, Structure, and Properties of {(Me₃Si)₂CH}₂SnH(OH)
  作者：Frank Schager、Richard Goddard、Klaus Seevogel、Klaus-Richard Pörschke

  DOI：10.1021/om970997n

  日期：1998.4.1

  The Lappert stannylene SnR2, R = CH(SiMe3)2, adds water and methanol to yield the low-melting-point, crystalline hydroxy- and methoxydiorganostannanes R2SnH(OH) (1) and R2SnH(OMe) (2). The corresponding deuterated derivatives R2SnD(OD) (1-d2) and R2SnD(OCD3) (2-d4) have also been prepared. Compounds 1 and 2 react with D2O with retention of the Sn−H bond to give R2SnH(OD) (1-d(SnOD)). The reaction is

  拉珀特亚锡SnR 2（R = CH（SiMe 3）2）加入水和甲醇，得到低熔点的结晶羟基和甲氧基二有机锡烷烃R 2 SnH（OH）（1）和R 2 SnH（OMe）（2）。还制备了相应的氘代衍生物R 2 SnD（OD）（1 - d 2）和R 2 SnD（OCD 3）（2 - d 4）。化合物1和2与D 2 O反应，保留Sn-H键，得到R 2SnH（OD）（1 - d（SnOD））。该反应被认为是通过[R 2 SnH（OR'）2 ] -（R'＝ H，D或Me）的中间或过渡状态通过S N 2型机理进行的。与此相一致，2 - d 4被水解为R 2 SnD（OH）（1 - d（SnD））。对1的单晶X射线结构分析表明，单个分子在具有短OH···O *氢桥（O···O * = 2.854（2）Å）的固体中形成C i对称二聚体。 。1与（i Pr的反应2 PC 2 H 4 P i Pr 2）Pd（C 2
• Preparation and Structural Characterization of the Palladium(0)−Carbonyl Complexes (R₂PC₂H₄PR₂)Pd(CO)₂ and {(R₂PC₂H₄PR₂)Pd}₂(μ-CO)
  作者：Roman Trebbe、Richard Goddard、Anna Rufińska、Klaus Seevogel、Klaus-Richard Pörschke

  DOI：10.1021/om990239s

  日期：1999.6.1

  (dippe)Pd(C2H4) and (dtbpe)Pd(C2H4) react with an excess of CO to afford the novel tetrahedral Pd0−dicarbonyl complexes (dippe)Pd(CO)2 (1) and (dtbpe)Pd(CO)2 (2). Partial CO elimination from 2 yields dinuclear (dtbpe)Pd}2(μ-CO) (3), containing a single bridging carbonyl ligand. 3 represents the smallest cluster containing the Pd2(μ-CO) group and, as such, is also the simplest model compound for CO adsorption

  （d i ppe）Pd（C 2 H 4）和（d t bpe）Pd（C 2 H 4）与过量的CO反应生成新颖的四面体Pd 0-二羰基配合物（d i ppe）Pd（CO）2（1）和（d t bpe）Pd（CO）2（2）。从2中除去部分CO会生成双核（d t bpe）Pd} 2（μ-CO）（3），其中包含一个桥接的羰基配体。3表示包含Pd 2的最小簇（μ-CO）基团，因此也是在Pd（100）表面吸附CO的最简单模型化合物。热分解3产生被假设为双核物种（d游离羰基的产物吨BPE）的Pd} 2（4）。已经确定了2和3的分子结构，并且进一步通过CP-MAS NMR光谱对固体进行了表征。
• <i>cis</i>-(R‘₂PC₂H₄PR‘₂)PdH(SnR₃) Complexes:  Trapped Intermediates in the Palladium-Catalyzed Hydrostannation of Alkynes
  作者：Roman Trebbe、Frank Schager、Richard Goddard、Klaus-Richard Pörschke

  DOI：10.1021/om9908128

  日期：2000.2.1

  The complexes (R'2PC2H4PR'(2))Pd(C2H4) (R' = Pr-i, Bu-t) react with R3SnH (R = Me, Bu-n) by displacement of the ethene ligand and oxidative addition of the Sn-H bond to generate the chelating phosphane stabilized cis Pd-II hydride stannyl complexes (R'2PC2H4PR'(2))PdH(SnR3) (R' = Pr-i (1), Bu-t (2)). Complex 1a (R' = Pr-i, R = Me), containing the smallest substituents, is only transiently formed but has been detected at -80 degrees C by NMR spectroscopy. It reacts further with Me3SnH, even at -120 degrees C, by eliminating hydrogen to give (d(i)ppe)Pd(SnMe3)(2) (3). In contrast, the isolated (d(i)ppe)PdH((SnBu3)-Bu-n) (Pb) is briefly stable at ambient temperature, whereas the sterically encumbered species (d(t)bpe)PdH(SnR3) (R = Me (2a), Bu-n (2b)) are stable well above 100 degrees C. The molecular structure of 2a has been determined by X-ray crystallography. Complex 2a reacts with 2 equiv of C2R "(2) (R " = CO2Me) to give (d(t)bpe)Pd(C2R "(2)) (4) and predominantly the corresponding (E)-vinylstannane (E)-(R ")(H)C=C(SnMe3)(R ") (E-5). Since 2a also catalyzes the hydrostannation of the alkyne, the cis Pd-II hydride stannyl complexes 1a,b and 2a,b represent trapped intermediates in the Pd-catalyzed hydrostannation of alkynes. The existence of the complexes also sheds light on the mechanism of the Pd-catalyzed degradation of R3SnH into Sn2R6 and H-2.
• A Palladium-Catalyzed Stannole Synthesis
  作者：Jochen Krause、Karl-Josef Haack、Klaus-Richard Pörschke、Barbara Gabor、Richard Goddard、Christian Pluta、Klaus Seevogel

  DOI：10.1021/ja952495b

  日期：1996.1.1

  A palladium-catalyzed (2 + 2 + 1) cycloaddition reaction of two C2H2 and one SnR(2) to form C-unsubstituted stannoles (C4H4)SnR(2) [R = CH(SiMe(3))(2) 2a, R(2) = C(SiMe(3))(2)CH2}(2) 2c] is described. Catalysts are (R'(2)PC(2)H(4)PR'(2))Pd complexes (slow reaction) and (R'P-3)(2)Pd complexes (fast reaction). The mechanism of the catalysis has been elucidated in detail from stoichiometric reactions based on R = CH(SiMe(3))(2). For the [(R'(2)PC(2)H(4)PR'(2))Pd]-catalyzed system, the starting Pd(0)-ethene complexes (R'(2)PC(2)H(4)PR'(2))Pd(C2H4) (R' = Pr-i (3),(t)Bu (4)) react both with ethyne to give the Pd(0)-ethyne derivatives (R'(2)PC(2)H(4)PR'(2))Pd(C2H2) (R' = Pr-i (5), (t)Bu (6)) and with SnR(2) to yield the Pd(0)-Sn(II) adducts (R'(2)PC(2)H(4)PR'(2))Pd=SnR(2) (R' = Pr-i (7), (t)Bu (8)). The Pd-Sn bond [2.481(2) Angstrom] of 7 is very short, indicative of partial multiple bonding. Subsequent reactions of the Pd(0)-ethyne complexes 5 and 6 with SnR(2) or of the Pd(0)-Sn(II) complexes 7 and 8 with ethyne afford the 1,2-palladastannete complexes (R'2PC2H4-PR'(2))Pd(CH=CH)SnR(2) (Pd-Sn) (R' = Pr-i (10), (t)Bu (11)). The derivative with R' = Me (9) has also been synthesized. In 10 a Pd-Sn single bond [2.670(1) Angstrom] is present. Complexes 10 and 11 (as well as 7 and 8 but not 9) react slowly with additional ethyne at 20 degrees C to reform the Pd(0)-ethyne complexes 5 and 6 with concomitant generation of the stannole (C4H4)SnR(2) (2a). Likely intermediates of this reaction are the Pd(0)-eta(2)-stannole complexes (R'(2)PC(2)H(4)PR'(2))Pd(eta(2)-C(4)H(4)SnR(2)) (R' = Pr-i (12), (t)Bu (13)), which have been synthesized independently. The stannole ligand in 12, 13 is easily displaced by ethyne to yield 5 or 6 or by SnR(2) to yield 7 or 8. Thus, the isolated complexes 5-8 and 10-13 are conceivable intermediates of the catalytic stannole formation, and from their stoichiometric reactions the catalysis cycle can be assembled. For the [(R'P-3)(2)Pd]-catayyze system, the corresponding intermediates (Me(3)P)(2)Pd(C2H2) (15), ((Pr3P)-Pr-i)(2)Pd(C2H2) (17), (Me(3)P)(2)Pd=SnR(2) (18), ((Pr3P)-Pr-i)(2)Pd=SnR(2) (20), and (Me(3)P)(2)Pd(CH=CH)SnR(2) (Pd-Sn) (19) have been isolated or detected by NMR, and ((Pr3P)-Pr-i)(2)Pd(CH=CH)SnR(2) (Pd-Sn) (21) is postulated as an intermediate. The [(Me(3)P)(2)Pd] system (stannole formation above 0 degrees C) is catalytically more active than any of the [(R'(2)PC(2)H(4)PR'(2))Pd] systems (slow stannole formation for R' = (t)Bu at 20 degrees C). Most active is the [((Pr3P)-Pr-i)(2)Pd] system, allowing a catalytic synthesis of the stannole 2a from SnR(2) and ethyne at -30 degrees C [1% of 17; yield 2a: 87%; TON (turnover number): 87].By carrying out the catalysis in pentane at 20 degrees C (0.04% of 17), the TON is increased to 1074 but the yield of 2a is diminished to 43% due to uncatalyzed thermal side reactions.