[Cy2PH2]Cl

• 分子结构分类: 有机化合物 - 有机磷化合物
• 英文名称: [Cy2PH2]Cl
• 英文别名: Dicyclohexylphosphanium;chloride；dicyclohexylphosphanium;chloride
• 化学式: C₁₂H₂₄P*Cl
• 分子量: 234.749
• InChiKey: WDOKISJWRVNYNS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.75
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  1
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  [Cy2PH2]Cl 以 乙醚 、 甲苯 为溶剂， 生成 (dicyclohexylphosphino)borane
  参考文献：
  名称：

  过渡金属催化的膦-Gallane加合物的离解：机理模型配合物的分离和非均相催化剂中毒研究。

  摘要：

  试图通过用约3-6的处理来诱导膦-Gallane加合物Cy2PH.GaH3（Cy = cyclohexyl）（1）的催化脱氢偶联。5 mol％的Rh（I）络合物[{Rh（mu-Cl）（1,5-cod）} 2]（cod =环辛二烯）或Rh（0）物种Rh / Al2O3和[Oct4N] Cl-稳定的胶体Rh导致催化的P-Ga键断裂，生成膦，H2和Ga金属。有趣的是，随后用Me 2 NH.BH 3处理反应混合物未能通过Rh催化的脱氢偶联形成[Me 2 N-BH 2] 2，这表明发生了催化剂失活。涉及用Cy2PH，PMe3或GaH3.OEt2处理活性Rh（0）催化剂的中毒研究表明，由于Me2NH.BH3的脱氢偶联速率显着降低或根本没有发生，因此确实发生了失活。经Cy2PH和PMe3处理的胶体Rh（0）的X射线光电子能谱分析证实，在每种情况下，催化剂表面均存在磷，这与通过膦连接而引起的催化剂中毒相一致。提出了1和Me3P

  DOI：

  10.1021/ic700573j

文献信息

• [EN] BIDENTATE CHIRAL LIGANDS FOR USE IN CATALYTIC ASYMMETRIC ADDITION REACTIONS<br/>[FR] LIGANDS CHIRAUX BIDENTATES UTILISABLES DANS DES RÉACTIONS D'ADDITION CATALYTIQUES ASYMÉTRIQUES
  申请人：SOLVIAS AG

  公开号：WO2009065784A1

  公开（公告）日：2009-05-28

  Compounds of the formula (I), in the form of mixtures comprising predominantly one diastereomer or in the form of pure diastereomers, Z1-Q-P*R0R1 (I) in which Z1 is a C-bonded, secondary phosphine group -P(R)2; in which R is in each case independently hydrocarbon radicals or heterohydrocarbon radicals, or Z1 is the -P*R0R1 group; Q is a bivalent, achiral, aromatic base skeleton, a bivalent, achiral ferrocene base skeleton, an optionally substituted bivalent cycloalkane or heterocycloalkane skeleton, or a C1-C4-alkylene skeleton, and in which base skeletons a secondary phosphine group Z1 is bonded directly to a carbon atom, or, in the case of cyclic base skeletons, directly to a carbon atom or via a C1-C4-alkylene group, and in which base skeletons a P-chiral group -P*R0R1 is bonded directly to a carbon atom, or, in the case of cyclic base skeletons, directly to a carbon atom or via a C1-C4-alkylene group to a carbon atom such that the phosphorus atoms are linked via 1 to 7 atoms of a carbon chain optionally interrupted by heteroatoms from the group of O, S, N, Fe or Si; P* is a chiral phosphorus atom; R0 is methyl or hydroxyl, and R0 is methyl when Z1 is the -P*R0R1 group; and R1 is a C-bonded optically enriched or optically pure chiral, mono- or polycyclic, nonaromatic hydrocarbon or heterohydrocarbon radical which has 3 to 12 ring atoms and 1 to 4 rings and which has a stereogenic carbon atom at least in the α position to the P-C bond; Metal complexes of these ligands are homogeneous catalysts for asymmetric addition reactions, particularly hydrogenations.

  化合物的公式（I）的形式，以主要包含一种对映异构体的混合物形式或纯对映异构体的形式，Z1-Q-P*R0R1（I），其中Z1是C-键合的次磷酸基团-P（R）2；其中R分别是烃基或杂烃基，或Z1是-P*R0R1基团；Q是二价的、不对映的、芳香基骨架，二价的、不对映的二茂铁基骨架，一个可选择取代的二价环烷烃或杂环烷烃骨架，或一个C1-C4-烷基骨架，并且在这些基骨架中，次磷酸基团Z1直接键合到一个碳原子，或者在环状基骨架的情况下，直接键合到一个碳原子或通过一个C1-C4-烷基团，以及在这些基骨架中，一个P-手性基团-P*R0R1直接键合到一个碳原子，或者在环状基骨架的情况下，直接键合到一个碳原子或通过一个C1-C4-烷基团到一个碳原子，以使磷原子通过1到7个碳链原子连接，这些碳链原子可以通过来自O、S、N、Fe或Si的杂原子间断连接；P*是一个手性磷原子；R0是甲基或羟基，当Z1是-P*R0R1基团时，R0是甲基；R1是一个C-键合的光学富集或光学纯的手性、单环或多环、非芳香烃基或杂烃基，具有3到12个环原子和1到4个环，并且至少在P-C键的α位置具有一个立体异构碳原子；这些配体的金属络合物是用于不对称加成反应的均相催化剂，特别是氢化反应。
• [EN] PHOSPHINYL FORMAMIDINE COMPOUNDS, METAL COMPLEXES, CATALYST SYSTEMS, AND THEIR USE TO OLIGOMERIZE OR POLYMERIZE OLEFINS<br/>[FR] COMPOSÉS PHOSPHINYL FORMAMIDINE, COMPLEXES MÉTALLIQUES, SYSTÈMES DE CATALYSEUR, ET LEUR UTILISATION POUR OLIGOMÉRISER OU POLYMÉRISER DES OLÉFINES
  申请人：CHEVRON PHILLIPS CHEMICAL CO

  公开号：WO2015094207A1

  公开（公告）日：2015-06-25

  N2-phosphinyl formamidine compounds and N2-phosphinyl formamidine metal salt complexes are described. Methods for making N2-phosphinyl formamidine compounds and N2-phosphinyl formamidine metal salt complexes are also disclosed. Catalyst systems utilizing the N2-phosphinyl formamidine metal salt complexes are also disclosed along with the use of the N2-phosphinyl amidine compounds and N2- phosphinyl amidinate metal salt complexes for the oligomerization and/or polymerization of olefins.

  描述了N2-磷酰基甲酰胺化合物和N2-磷酰基甲酰胺金属盐配合物。还公开了制备N2-磷酰基甲酰胺化合物和N2-磷酰基甲酰胺金属盐配合物的方法。还公开了利用N2-磷酰基甲酰胺金属盐配合物的催化剂体系，以及利用N2-磷酰基胺化合物和N2-磷酰基胺金属盐配合物进行烯烃的寡聚和/或聚合的用途。
• Ferrocenediphosphines
  申请人：Chen Weiping

  公开号：US20090124812A1

  公开（公告）日：2009-05-14

  Compounds of the formula I in the form of enantiomerically pure diastereomers or a mixture of diastereomers, (I), where the radicals R 1 are identical or different and are each C 1 -C 4 -alkyl; m is 0 or an integer from 1 to 3; n is 0 or an integer from 1 to 4; R 2 is a hydrocarbon radical or a C-bonded heterohydrocarbon radical; Cp is unsubstituted or C 1 -C 4 -alkyl-substituted cyclopentadienyl; Y is a C-bonded chiral group which directs metals of metallation reagents into the ortho position; and Phos is a P-bonded P(III) substituent. The compounds are chiral ligands for complexes of transition metals which are used as homogeneous catalysts in asymmetric syntheses.

  化学式为I的化合物形式为对映纯的非对映异构体或非对映异构体的混合物，其中基团R1相同或不同，且均为C1-C4烷基；m为0或1至3的整数；n为0或1至4的整数；R2为碳氢基团或C键结合的杂环碳氢基团；Cp为未取代或C1-C4烷基取代的环戊二烯基；Y为C键结合的手性基团，可将金属化试剂导向邻位位置；Phos为P键结合的P（III）取代基。这些化合物是过渡金属配合物的手性配体，用作不对称合成中的均相催化剂。
• Diphosphine ligands
  申请人：Pugin Benoit

  公开号：US20100029967A1

  公开（公告）日：2010-02-04

  Compounds of the formulae I and Ia in the form of mixtures of diastereomers or pure diastereomers, (I), (Ia), where R 1 is a hydrogen atom or C 1 -C 4 -alkyl and R′ 1 is C 1 -C 4 -alkyl; X 1 and X 2 are each, independently of one another, a sec-phosphino group; T is C 6 -C 20 -arylene or C 4 -C 18 -heteroarylene having heteroatoms selected from the group consisting of O, S, —N═ and N(C 1 -C 4 -alkyl); v is 0 or an integer from 1 to 4; X 1 is bound in the ortho position relative to the T-C* bond; Q is vinyl, methyl, ethyl, —CH 2 —OR, —CH 2 —N(C 1 -C 4 -alkyl) 2 or a C- or S-bonded chiral group which directs metals of metallation reagents into the ortho position; R is hydrogen, a silyl radical or an aliphatic, cycloaliphatic, aromatic or aromatic-aliphatic hydrocarbon radical which has from 1 to 18 carbon atoms and is unsubstituted or substituted by C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, F or CF 3 ; are ligands for metal complexes as homogeneous catalyst in asymmetric syntheses.

  公式I和Ia的化合物，以对映异构体的混合物或纯对映体的形式存在，其中R1为氢原子或C1-C4-烷基，R′1为C1-C4-烷基; X1和X2分别是独立的二级膦基团; T是C6-C20-芳基或C4-C18-杂芳基，其中杂原子选自O，S，—N═和N（C1-C4-烷基）; v为0或1至4的整数; X1与T-C*键相对的正交位置结合; Q为乙烯基，甲基，乙基，—CH2—OR，— —N（C1-C4-烷基）2或C-或S-键合的手性基团，可将金属化反应物导入正交位置; R为氢，硅基自由基或具有1至18个碳原子的脂肪族，环脂族，芳香族或芳香族-脂肪族碳氢基团，未取代或被C1-C4-烷基，C1-C4-烷氧基，F或CF3取代; 是金属络合物的配体，用于不对称合成中的均相催化剂。
• BIDENTATE CHIRAL LIGANDS FOR USE IN CATALYTIC ASYMMETRIC ADDITION REACTIONS
  申请人：Pugin Benoît

  公开号：US20110118482A1

  公开（公告）日：2011-05-19

  Compounds of the formula (I), in the form of mixtures comprising predominantly one diastereomer or in the form of pure diastereomers, Z 1 -Q-P*R 0 R 1 (I) in which Z 1 is a C-bonded, secondary phosphine group —P(R) 2 ; in which R is in each case independently hydrocarbon radicals or heterohydrocarbon radicals, or Z 1 is the —P*R 0 R 1 group; Q is a bivalent, achiral, aromatic base skeleton, a bivalent, achiral ferrocene base skeleton, an optionally substituted bivalent cycloalkane or heterocycloalkane skeleton, or a C 1 -C 4 -alkylene skeleton, and in which base skeletons a secondary phosphine group Z 1 is bonded directly to a carbon atom, or, in the case of cyclic base skeletons, directly to a carbon atom or via a C 1 -C 4 -alkylene group, and in which base skeletons a P-chiral group —P*R 0 R 1 is bonded directly to a carbon atom, or, in the case of cyclic base skeletons, directly to a carbon atom or via a C 1 -C 4 -alkylene group to a carbon atom such that the phosphorus atoms are linked via 1 to 7 atoms of a carbon chain optionally interrupted by heteroatoms from the group of O, S, N, Fe or Si; P* is a chiral phosphorus atom; R 0 is methyl or hydroxyl, and R 0 is methyl when Z 1 is the —P*R 0 R 1 group; and R 1 is a C-bonded optically enriched or optically pure chiral, mono- or polycyclic, nonaromatic hydrocarbon or heterohydrocarbon radical which has 3 to 12 ring atoms and 1 to 4 rings and which has a stereogenic carbon atom at least in the a position to the P—C bond; Metal complexes of these ligands are homogeneous catalysts for asymmetric addition reactions, particularly hydrogenations.

  化合物的结构式（I），以主要由一个对映异构体组成的混合物形式或纯对映异构体形式出现，其中Z1是一个C-键结合的次级膦基团- P（R）2；其中R在每种情况下独立地是碳氢基团或杂环碳氢基团，或Z1是-P * R0R1基团；Q是双价的、无手性的、芳香基骨架、双价的、无手性的二茂铁基骨架、可选地取代的双价环烷基或杂环烷基骨架，或C1-C4-烷基骨架，在这些基骨架中，次级膦基团Z1直接键合到一个碳原子上，或在环状基骨架的情况下，直接键合到一个碳原子或通过C1-C4-烷基骨架键合到一个碳原子上，且在这些基骨架中，P-手性基团-P * R0R1直接键合到一个碳原子上，或在环状基骨架的情况下，直接键合到一个碳原子或通过C1-C4-烷基骨架键合到一个碳原子，使得磷原子通过1到7个碳链原子（可选地由O、S、N、Fe或Si的杂原子中断）相连；P *是一个手性磷原子；R0是甲基或羟基，当Z1是-P * R0R1基团时，R0为甲基；R1是C-键结合的光学纯或光学富集的手性、单环或多环、非芳香碳氢或杂环碳氢基团，具有3到12个环原子和1到4个环，并且在P-C键的α位至少有一个立体异构碳原子；这些配体的金属络合物是不对称加成反应的均相催化剂，特别是氢化反应。