Tris(undec-10-enyl)phosphane | 1241848-62-3

• 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: Tris(undec-10-enyl)phosphane
• 英文别名: tris(undec-10-enyl)phosphane
• CAS: 1241848-62-3
• 化学式: C₃₃H₆₃P
• 分子量: 490.837
• InChiKey: NLXRGMVMYYPYFG-UHFFFAOYSA-N

物化性质

• 沸点：
  549.1±19.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  13.5
• 重原子数：
  34
• 可旋转键数：
  30
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.82
• 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：

  Tris(undec-10-enyl)phosphane 在 Grubbs catalyst first generation 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 20.0~50.0 ℃ 、500.01 kPa 条件下， 反应 144.0h， 生成
  参考文献：
  名称：

  Syntheses, Structures, and Thermal Properties of Gyroscope-like Complexes Consisting of PtCl₂ Rotators Encased in Macrocyclic Dibridgehead Diphosphines P((CH₂)_n)₃P with Extended Methylene Chains (n = 20/22/30) and Isomers Thereof

  摘要：

  Reactions of P((CH2)(m)CH=CH2)(3) (2.0 equiv; m = 9 (f), 10 (g), 14 (k)) and PtCl2 in toluene give trans-PtCl2(P((CH2),CH=CH2)(3))(2) (trans-1f,g,k; 63-49%). Reactions of trans-lf,g with Grubbs first generation catalyst (CH2Cl2/reflux) followed by hydrogenations (cat. PtO2) afford chromatographically separable gyroscope-like trans-(GRAPHICS) (trans-2f,g, 3-19%; from interligand metathesis) and trans-(GRAPHICS) (trans-2'f,g, 25-12%; from inter and intraligand metathesis), where n = 2m + 2. Under analogous conditions, trans-1k gives only cis-(GRAPHICS) (cis-2k, 39%), but when o-C6H4CL2 solutions are kept at 180 C, trans-2k forms (quantitative by P-31 NMR; 72% isolated). In contrast, a similar sequence with the Hoveyda-Grubbs second generation catalyst gives only trans-2k (8%). The stability order cis > trans is established for lg and 2'f,g in CH2Cl2 (61-56:39-44; months at RT), but the opposite is found for lg and 2'f in toluene (9-7:91-93) or 2'f in o-C6H4Cl2 (7:93). Thus, it is proposed that the conversion of trans-lk to cis-2k involves a geometrical isomerization of the educt or an intermediate catalyzed by a species derived from Grubbs catalyst. The crystal structures of trans-2gTHF and cis-2'f,g are determined and analyzed in detail.

  DOI：

  10.1021/acs.organomet.8b00345
• 作为产物：
  描述：

  11-溴-1-十一烯 在 magnesium 、 三氯化磷 作用下， 以 乙醚 为溶剂， 生成 Tris(undec-10-enyl)phosphane
  参考文献：
  名称：

  新型螯合膦连接基系统的合成，固定化，MAS和HR-MAS NMR及其铑加合物的催化作用

  摘要：

  一类新的三齿膦配位体的具有通式[MeP的{（CH 2）X PPH 2 } 3 ] +我-（X = 4，7，11）和[MeP的（CH 2 PPH 2）3 ] +光学传递函数-，已经合成并具有充分的特征。接头已通过其via部分固定在二氧化硅上通过固态HR-MAS（高分辨率魔角旋转）NMR在各种溶剂中研究了静电相互作用及其迁移和浸出。固定化的威尔金森型铑配合物是通过与表面结合的连接子进行配体交换而获得的。已经针对1-十二碳烯的氢化测试了催化剂的活性和寿命。通过固定接头[MeP的{（CH结合的铑催化剂前体2）7 PPH 2 } 3 ] +我-导致活性和寿命最高的材料，可以分批回收30次。其他催化剂显示较短的寿命。对于所有催化剂，已经证明形成了具有约4nm的窄尺寸分布的铑纳米颗粒。

  DOI：

  10.1002/adsc.201000585

文献信息

• Three-Fold Intramolecular Ring Closing Alkene Metatheses of Square Planar Complexes with <i>cis</i> Phosphorus Donor Ligands P(X(CH₂)_<i>m</i>CH═CH₂)₃ (X = −, <i>m</i> = 5–10; X = O, <i>m</i> = 3–5): Syntheses, Structures, and Thermal Properties of Macrocyclic Dibridgehead Diphosphorus Complexes
  作者：Hemant Joshi、Sugam Kharel、Andreas Ehnbom、Katrin Skopek、Gisela D. Hess、Tobias Fiedler、Frank Hampel、Nattamai Bhuvanesh、John A. Gladysz

  DOI：10.1021/jacs.8b02846

  日期：2018.7.11

  analogous conditions, establishing the stability order trans > cis. Similar metathesis/hydrogenation sequences with octahedral complexes containing two cis phosphine ligands, fac-ReX(CO)3(P((CH2)6CH═CH2)3)2 (X = Cl, Br), give fac- ReX(CO)3( P(CH2)13 CH2)((CH2)14)( P(CH2)13 CH2) (19-50%), which are derived from a combination of interligand and intraligand metathesis. The relative stabilities of cis/ trans

  顺式 PtCl2(P((CH2) mCH=CH2)3)2 和 Grubbs 的第一代催化剂反应，然后氢化得到顺式 PtCl2(P((CH2) n)3 P) ( cis-2; n = 2 m + 2 = 12 (b)、14 (c)、16 (d)、18 (e)、20 (f)、22 (g)；6-40%)，源自3倍配体间复分解。亚磷酸盐配合物 cis-PtCl2(P(O(CH2) m*CH=CH2)3)2 类似地转化为顺式 PtCl2(P(O(CH2) n*O)3 P) ( cis-5; n* = 8 (a)、10 (b)、12 (c)、10-20%)。取代产物 cis-PtPh2(P((CH2) n)3 P) (cis-6c,d) 和 cis-PtI2(P(O(CH2)10O)3 P) 分别使用 Ph2Zn 和 NaI 制备。cis-2c,d,f, cis-5a,b 和 cis-6c 的晶体结构
• Syntheses and Palladium, Platinum, and Borane Adducts of Symmetrical Trialkylphosphines with Three Terminal Vinyl Groups, P((CH₂)_mCH=CH₂)₃
  作者：Agnieszka J. Nawara-Hultzsch、Katrin Skopek、Takanori Shima、Michał Barbasiewicz、Gisela D Hess、Dirk Skaper、John A Gladysz

  DOI：10.1515/znb-2010-0327

  日期：2010.3.1

  Reactions of Br(CH₂)_mCH=CH₂ with Mg powder and then PCl₃ (0.33 equiv.) afford P((CH₂)_m- CH=CH₂)₃ (1; m = a, 4; b, 5; c, 6; d, 7; e, 8; f, 9; 52 - 87%). Reactions of 1a - c, e with PdX₂(COD) (X = Cl, Br) give trans-PdX₂(P((CH₂)_mCH=CH₂)₃)₂ (35 - 92%). Reactions of 1b - e with PtCl₂ in benzene give mainly trans-PtCl₂(P((CH₂)mCH=CH₂)₃)₂ (trans-5b-e; 52 - 75%), whereas those with K₂PtCl₄ in water give mainly cis-5b-e (33 - 70%). The reaction of equimolar quantities of 1c and H₃B・S(CH₃)₂ gives the 1 : 1 adduct H₃B・P((CH₂)₆CH=CH₂)₃ (85%). In none of these transformations are by-products derived from the C=C linkages observed

  Br(CH₂)ₘCH=CH₂与镁粉和PCl₃（0.33当量）的反应得到P((CH₂)ₘ- CH=CH₂)₃（1; m = a, 4; b, 5; c, 6; d, 7; e, 8; f, 9; 52 - 87％）。1a - c, e与PdX₂(COD)（X = Cl, Br）反应得到反式-PdX₂(P((CH₂)ₘCH=CH₂)₃)₂（35 - 92％）。1b - e与PtCl₂在苯中反应主要得到反式-PtCl₂(P((CH₂)ₘCH=CH₂)₃)₂（反-5b-e; 52 - 75％），而与K₂PtCl₄在水中反应主要得到顺式-5b-e（33 - 70％）。1c和H₃B・S(CH₃)₂等量反应得到1：1加合物H₃B・P((CH₂)₆CH=CH₂)₃（85％）。在这些转化中，没有观察到来自C=C键的副产物。
• Synthesis, Immobilization, MAS and HR-MAS NMR of a New Chelate Phosphine Linker System, and Catalysis by Rhodium Adducts Thereof
  作者：J. Guenther、J. Reibenspies、J. Blümel

  DOI：10.1002/adsc.201000585

  日期：2011.2.11

  in various solvents. Immobilized Wilkinson-type rhodium complexes have been obtained by ligand exchange with the surface-bound linkers. The activities and lifetimes of the catalysts have been tested with respect to the hydrogenation of 1-dodecene. The rhodium catalyst precursor bound by the immobilized linker [MeP(CH2)7PPh2}3]+I− led to material with the highest activity and lifetime, and it could be

  一类新的三齿膦配位体的具有通式[MeP的（CH 2）X PPH 2 } 3 ] +我-（X = 4，7，11）和[MeP的（CH 2 PPH 2）3 ] +光学传递函数-，已经合成并具有充分的特征。接头已通过其via部分固定在二氧化硅上通过固态HR-MAS（高分辨率魔角旋转）NMR在各种溶剂中研究了静电相互作用及其迁移和浸出。固定化的威尔金森型铑配合物是通过与表面结合的连接子进行配体交换而获得的。已经针对1-十二碳烯的氢化测试了催化剂的活性和寿命。通过固定接头[MeP的（CH结合的铑催化剂前体2）7 PPH 2 } 3 ] +我-导致活性和寿命最高的材料，可以分批回收30次。其他催化剂显示较短的寿命。对于所有催化剂，已经证明形成了具有约4nm的窄尺寸分布的铑纳米颗粒。
• Syntheses, Structures, and Thermal Properties of Gyroscope-like Complexes Consisting of PtCl₂ Rotators Encased in Macrocyclic Dibridgehead Diphosphines P((CH₂)_<i>n</i>)₃P with Extended Methylene Chains (<i>n</i> = 20/22/30) and Isomers Thereof
  作者：Sugam Kharel、Hemant Joshi、Nattamai Bhuvanesh、John A. Gladysz

  DOI：10.1021/acs.organomet.8b00345

  日期：2018.9.24

  Reactions of P((CH2)(m)CH=CH2)(3) (2.0 equiv; m = 9 (f), 10 (g), 14 (k)) and PtCl2 in toluene give trans-PtCl2(P((CH2),CH=CH2)(3))(2) (trans-1f,g,k; 63-49%). Reactions of trans-lf,g with Grubbs first generation catalyst (CH2Cl2/reflux) followed by hydrogenations (cat. PtO2) afford chromatographically separable gyroscope-like trans-(GRAPHICS) (trans-2f,g, 3-19%; from interligand metathesis) and trans-(GRAPHICS) (trans-2'f,g, 25-12%; from inter and intraligand metathesis), where n = 2m + 2. Under analogous conditions, trans-1k gives only cis-(GRAPHICS) (cis-2k, 39%), but when o-C6H4CL2 solutions are kept at 180 C, trans-2k forms (quantitative by P-31 NMR; 72% isolated). In contrast, a similar sequence with the Hoveyda-Grubbs second generation catalyst gives only trans-2k (8%). The stability order cis > trans is established for lg and 2'f,g in CH2Cl2 (61-56:39-44; months at RT), but the opposite is found for lg and 2'f in toluene (9-7:91-93) or 2'f in o-C6H4Cl2 (7:93). Thus, it is proposed that the conversion of trans-lk to cis-2k involves a geometrical isomerization of the educt or an intermediate catalyzed by a species derived from Grubbs catalyst. The crystal structures of trans-2gTHF and cis-2'f,g are determined and analyzed in detail.