双[1,3-双(二异丙基膦)丙烷]钯 | 123333-45-9

• 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
• 中文名称: 双[1,3-双(二异丙基膦)丙烷]钯
• 中文别名: [P，P''-1,3-双（二异丙基膦基）丙烷][P-1,3-双（二异丙基膦基）丙烷]钯（0）
• 英文名称: Pd(1,3-bis(diisopropylphosphino)propane)2
• 英文别名: (1,3-bis(di-isopropylphosphino)propane)2Pd(0)；3-di(propan-2-yl)phosphanylpropyl-di(propan-2-yl)phosphane;palladium
• CAS: 123333-45-9
• 化学式: C₃₀H₆₈P₄Pd
• 分子量: 659.185
• InChiKey: OYTRFAKJOIUDDD-UHFFFAOYSA-N

物化性质

• 稳定性/保质期：
  <p>遵照规定使用和储存，则不会分解。</p>

计算性质

• 辛醇/水分配系数(LogP)：
  11.95
• 重原子数：
  35
• 可旋转键数：
  16
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

安全信息

• 安全说明：
  S26
• 危险类别码：
  R36/37/38

反应信息

• 作为反应物：
  描述：

  双[1,3-双(二异丙基膦)丙烷]钯 在 盐酸 、 一氧化碳 作用下， 以 四氢呋喃 为溶剂， 生成
  参考文献：
  名称：

  A binuclear palladium(I) hydride. Formation, reactions, and catalysis

  摘要：

  (dippp)Pd(Ph)Cl (3) reacts with methanol to yield the novel hydrido Pd(I) dimer {[(dippp)-Pd]2(mu-H)(mu-CO)}+Cl- (1), (dippp)PdCl2 (4), H-2, benzene, and formaldehyde. In the presence of NEt3, HNEt3+Cl- is formed instead of 4. 1 can also be formed in a reaction of Pd(diPPP)2, HCl, and CO. Labeling studies and modeling reactions indicate that the novel transformation of 3 into 1 involves methanolysis of 3 followed by a beta-H elimination from a methoxo intermediate to yield formaldehyde, benzene, and the 14e transient (dippp)Pd (7). Formaldehyde decarbonylation, coupling of the palladium carbonyl complex with 7, and protonation lead to 1. Alternatively, 1 can be formed by electrophilic attack of protonated 7, on the carbonyl complex (dippp)Pd(CO). A number of reactivity modes have been identified for 1. Reaction with acetylenes results in bridge-splitting to form (dippp)Pd(eta2-acetylene) and in hydropalladation of the acetylene to form a vinyl complex. The hydropalladation process exhibits high regio- and stereoselectivity, resulting in cis addition and attachment of the Pd atom to the more hindered carbon, indicating electronic control. 1 undergoes exchange of the hydride for deuteride in CD3COCD3, most likely via an enol insertion into Pd-H. In the presence of an olefin, such as cyclooctene or ethyl vinyl ether, catalytic transfer deuteration takes place. Alpha-deuteration of the latter is preferred, indicating anti-Markovnikov Pd-H addition. The integrity of 1 is maintained during this process. With norbornene, bridge-splitting to form (dippp)Pd(norbornyl) (17) and its CO-insertion product 18 takes place. No H/D exchange catalysis is observed in this case with acetone-d6. 1 behaves as a Pd(0) complex and exhibits oxidative addition reactivity with chlorobenzene or benzylchloride, yielding (dippp)Pd(R)Cl. The relevance of this reactivity to Pd-catalyzed reactions is discussed.

  DOI：

  10.1021/om00014a035
• 作为产物：
  描述：

  {(dippp)Pd(η1-dippp)H}(1+)*OMe(1-) 以 甲醇 为溶剂， 生成 双[1,3-双(二异丙基膦)丙烷]钯
  参考文献：
  名称：

  A binuclear palladium(I) hydride. Formation, reactions, and catalysis

  摘要：

  (dippp)Pd(Ph)Cl (3) reacts with methanol to yield the novel hydrido Pd(I) dimer {[(dippp)-Pd]2(mu-H)(mu-CO)}+Cl- (1), (dippp)PdCl2 (4), H-2, benzene, and formaldehyde. In the presence of NEt3, HNEt3+Cl- is formed instead of 4. 1 can also be formed in a reaction of Pd(diPPP)2, HCl, and CO. Labeling studies and modeling reactions indicate that the novel transformation of 3 into 1 involves methanolysis of 3 followed by a beta-H elimination from a methoxo intermediate to yield formaldehyde, benzene, and the 14e transient (dippp)Pd (7). Formaldehyde decarbonylation, coupling of the palladium carbonyl complex with 7, and protonation lead to 1. Alternatively, 1 can be formed by electrophilic attack of protonated 7, on the carbonyl complex (dippp)Pd(CO). A number of reactivity modes have been identified for 1. Reaction with acetylenes results in bridge-splitting to form (dippp)Pd(eta2-acetylene) and in hydropalladation of the acetylene to form a vinyl complex. The hydropalladation process exhibits high regio- and stereoselectivity, resulting in cis addition and attachment of the Pd atom to the more hindered carbon, indicating electronic control. 1 undergoes exchange of the hydride for deuteride in CD3COCD3, most likely via an enol insertion into Pd-H. In the presence of an olefin, such as cyclooctene or ethyl vinyl ether, catalytic transfer deuteration takes place. Alpha-deuteration of the latter is preferred, indicating anti-Markovnikov Pd-H addition. The integrity of 1 is maintained during this process. With norbornene, bridge-splitting to form (dippp)Pd(norbornyl) (17) and its CO-insertion product 18 takes place. No H/D exchange catalysis is observed in this case with acetone-d6. 1 behaves as a Pd(0) complex and exhibits oxidative addition reactivity with chlorobenzene or benzylchloride, yielding (dippp)Pd(R)Cl. The relevance of this reactivity to Pd-catalyzed reactions is discussed.

  DOI：

  10.1021/om00014a035
• 作为试剂：
  描述：

  1-Methoxy-2-(dimethyl-alanoxy)-ethan 、 对硝基氯苯 在 双[1,3-双(二异丙基膦)丙烷]钯 作用下， 以 苯 为溶剂， 反应 22.0h， 以66%的产率得到4-硝基甲苯
  参考文献：
  名称：

  Palladium-Catalyzed Cross-Methylation of Aryl Chlorides by Stabilized Dimethylaluminium and -Gallium Reagents

  摘要：

  研究了两种使用分子内稳定的双烷基铝和镓复合物6-13进行钯催化的芳基氯交叉甲基化的方法。在第一种方法中，使用四（三苯基膦）钯（1）或二氯双（三苯基膦）钯（2）作为催化剂，在80-90°C下，通过向芳香环引入强吸电子基团来实现氯原子的活化。第二种方法基于应用[1,3-双（二异丙基膦）丙烷]钯（4）或相邻的富电子钯复合物作为催化剂。尽管4促进了芳基氯的平滑交叉烷基化，但无法活化简单的芳基溴。

  DOI：

  10.1055/s-2000-6373

文献信息

• Chelate-assisted, palladium-catalyzed efficient carbonylation of aryl chlorides
  作者：Yehoshua Ben-David、Moshe Portnoy、David Milstein

  DOI：10.1021/ja00205a039

  日期：1989.11
• Chelate effect on the structure and reactivity of electron-rich palladium complexes and its relevance to catalysis
  作者：Moshe Portnoy、David Milstein

  DOI：10.1021/om00029a025

  日期：1993.5

  In order to clarify the origin of the ''chelate effect' in catalysis by palladium, complexes of (Pr2P(CH2)nPr2P)-Pr-i-Pr-i (n = 2, dippe; n = 3, dippp; n = 4, dippb), Ph2P(CH2)3PPh2 (dppp), and PiPr2 nBu were prepared and their structures, dynamic properties, and reactivities were compared. Pd(dippe)2 1d is a coordinatively saturated complex, both in solution and in the solid state. X-ray characterization exhibits a distorted tetrahedral geometry. The dippe bite angle is 87.05-degrees. The compound crystallizes in the orthorhombic space group Pnna with a = 16.713(3) angstrom, b = 17.561(3) angstrom, c = 11.116(2) angstrom, V = 3277(1) angstrom3, Z = 4. Pd(dippp)2 (1a) and Pd(dippb)2 (1e) are coordinatively unsaturated, trigonal complexes and are in equilibrium with the binuclear complexes LPd(eta2-L)PdL, 1b and 1f, respectively. Whereas 1d does not exhibit dynamic behavior, 1a and 1e undergo fast, intramolecular phosphine exchange, a process which is not observed with 1b and 1f. The trigonal complexes (dippp)PdPiPr2Bu (1c) and (PiPr2nBu)3Pd were also prepared for comparison. The dippp complexes 1a-1c react with aryl chlorides to produce cis-(dippp)Pd(C6H4X)Cl as the major product and trans-(eta1-dipp)2Pd(C6H4X)Cl as the minor one (X = 4-OMe, 4-Me, H, 3-OMe, 4-COMe, 4-CHO, 4-NO2). In contrast, the dippb complex 1e oxidatively adds chlorobenzene to yield only the trans complex (eta1-dippb)2Pd(Ph)Cl. Reaction monitoring reveals that the cis and trans complexes are formed in parallel pathways. Cis/trans equilibrium is on the cis side for dippp and on the trans side for dippb. Reactivity toward chlorobenzene follows the trend Pd(dippp)2 > Pd(PiPr2nBu)3 >> Pd(dippe)2 >> Pd(dPPP)2. These results are interpreted in terms of chelate stability, ligand basicity, concentration of the active 14e species and effect of the P-Pd-P angle on its reactivity. The dippp ligand is unique in that it is the only one of those studied which results in Pd(0) complexes which (a) exhibit high reactivity in oxidative addition and (b) form cis complexes preferentially.
• Reactions of Electron-Rich Arylpalladium Complexes with Olefins. Origin of the Chelate Effect in Vinylation Catalysis
  作者：M. Portnoy、Y. Ben-David、I. Rousso、D. Milstein

  DOI：10.1021/om00021a021

  日期：1994.9

  Reaction of (dippp)Pd(Ph)Cl(1) with norbornene or styrene yields (dippp)PdCl2 (8) and (dippp)Pd(eta(2)-olefin). Kinetic follow-up reveals fast formation of (dippp)Pd(phenylnorbornyl)Cl (10), followed by its slow decomposition, with k(insertion) = 0.50 x 10(-3) L mol(-1) s(-1) and k(decomposition) = 0.90 X 10(-4) S-1. Phenylnorbornane and (with styrene) stilbenes are also formed. Faster reaction is observed with (dppp)Pd(Ph)Br (2) and faster still with (dippe)Pd(Cl (4) to yield, in the latter case, the stable (dippe)Pd(phenylnorbornyl)Cl (18). The rates of these reactions are strongly solvent dependent (DMF >> dioxane), are strongly retarded by added Cl-, and are unaffected by added phosphine, indicating that halide dissociation, followed by olefin coordination and rate-determining olefin insertion, are involved. In contrast, reaction of trans-(P(i)Pr(2)(n)Bu)(2)Pd(Ph)X (X = Cl, 5; X = Br, 6) with norbornene (or styrene) involves phosphine dissociation and leads to formation of (P(i)Pr(2)(n)Bu)(2)Pd(H)X. In the case of norbornene, beta-carbon elimination of the unobserved intermediate phenylnorbornyl complexes followed by beta-H elimination yields 1-methylene-2-phenylcyclohexenes. Complexes of the ligand dippb are unique in that both eta(1) and eta(2) coordination modes are easily accessible. While reaction products are similar to those obtained with dippp and dippe complexes, dependence of the reaction rate on reaction variables is intermediate between those observed for complexes of chelating and monodentate phosphines. The implications of these findings on catalysis are outlined.
• A binuclear palladium(I) hydride. Formation, reactions, and catalysis
  作者：Moshe Portnoy、David Milstein

  DOI：10.1021/om00014a035

  日期：1994.2

  (dippp)Pd(Ph)Cl (3) reacts with methanol to yield the novel hydrido Pd(I) dimer [(dippp)-Pd]2(mu-H)(mu-CO)}+Cl- (1), (dippp)PdCl2 (4), H-2, benzene, and formaldehyde. In the presence of NEt3, HNEt3+Cl- is formed instead of 4. 1 can also be formed in a reaction of Pd(diPPP)2, HCl, and CO. Labeling studies and modeling reactions indicate that the novel transformation of 3 into 1 involves methanolysis of 3 followed by a beta-H elimination from a methoxo intermediate to yield formaldehyde, benzene, and the 14e transient (dippp)Pd (7). Formaldehyde decarbonylation, coupling of the palladium carbonyl complex with 7, and protonation lead to 1. Alternatively, 1 can be formed by electrophilic attack of protonated 7, on the carbonyl complex (dippp)Pd(CO). A number of reactivity modes have been identified for 1. Reaction with acetylenes results in bridge-splitting to form (dippp)Pd(eta2-acetylene) and in hydropalladation of the acetylene to form a vinyl complex. The hydropalladation process exhibits high regio- and stereoselectivity, resulting in cis addition and attachment of the Pd atom to the more hindered carbon, indicating electronic control. 1 undergoes exchange of the hydride for deuteride in CD3COCD3, most likely via an enol insertion into Pd-H. In the presence of an olefin, such as cyclooctene or ethyl vinyl ether, catalytic transfer deuteration takes place. Alpha-deuteration of the latter is preferred, indicating anti-Markovnikov Pd-H addition. The integrity of 1 is maintained during this process. With norbornene, bridge-splitting to form (dippp)Pd(norbornyl) (17) and its CO-insertion product 18 takes place. No H/D exchange catalysis is observed in this case with acetone-d6. 1 behaves as a Pd(0) complex and exhibits oxidative addition reactivity with chlorobenzene or benzylchloride, yielding (dippp)Pd(R)Cl. The relevance of this reactivity to Pd-catalyzed reactions is discussed.