[(η6-C6Me6)RuCl2(DPVP)] | 265323-65-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [(η6-C6Me6)RuCl2(DPVP)]
• 英文别名: [(η6-C6Me6)Ru(diphenylvinylphosphine))Cl2]；[(η(6)-C6Me6)Ru(Ph2PCHCH2)Cl2]；[(η6-C6Me6)RuCl2(Ph2PCH=CH2)]；Dichlororuthenium;ethenyl(diphenyl)phosphane;1,2,3,4,5,6-hexamethylbenzene
• CAS: 265323-65-7
• 化学式: C₂₆H₃₁Cl₂PRu
• 分子量: 546.482
• InChiKey: JVNQBVHIKMZHDV-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  8.18
• 重原子数：
  30
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.23
• 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：

  [(η6-C6Me6)RuCl2(DPVP)] 在 tert-BuOK 作用下， 以 乙腈 为溶剂， 生成 [RuCl2(η1:η6-(3-pentamethylphenylpropyl)diphenylphosphine)]
  参考文献：
  名称：

  1,3,5-Me 3 C 6 H 3，p -MeC 6 H 4 CHMe 2，C 6 Me 6，p -MeC 6 H 4 Me和MeC 6 H 5与钌配位的碱促进的加氢烷基化反应（二）

  摘要：

  的[（η 6 -arene）的RuCl 2 ] 2（芳烃= 1,3,5-ME 3 Ç 6 ħ 3（1），p -MeC 6 ħ 4 CHME 2（2），C 6我6（3） ，p -MeC 6 ħ 4我（4），的MeC 6 H ^ 5（5））二聚体diphenylvinylphosphine（DPVP），以产生反应[（η 6 -1,3,5--ME 3 ç 6 ħ3）的Ru（DPVP）氯2 ]（1A），[（η 6 -对-的MeC 6 H ^ 4 CHME 2）的Ru（DPVP）氯2 ]（图2a），[（η 6 -C 6我6）的Ru（ DPVP）氯2 ]（图3a），[（η 6 - p -MeC 6 ħ 4 Me）中的Ru（DPVP）氯2 ]（图4a），和[（η 6 -MeC 6 ħ 5）的Ru（DPVP）氯2 ]（5a）。在乙腈中，化合物1 - 5发生碱促进的加氢烷基化反应用氢叔丁醇和diphenyl

  DOI：

  10.1021/om000375t
• 作为产物：
  描述：

  (RuCl2(η6-C6Me6))2 、 乙烯基二苯基膦 以 二氯甲烷 为溶剂， 以70.66%的产率得到[(η6-C6Me6)RuCl2(DPVP)]
  参考文献：
  名称：

  Synthesis and Characterization of [(η⁶-arene)Ru(R₃P)Cl₂] Complexes

  摘要：

  DOI：

  10.1080/00945710009351770

文献信息

• Scope and diastereoselectivity of intramolecular [4+2] Diels–Alder cycloaddition reactions of (η6-arene)Ru(DMPP)Cl2 complexes with dieneophilic ligands
  作者：Kent D Redwine、John H Nelson

  DOI：10.1016/s0022-328x(00)00504-0

  日期：2000.11

  C(O)Me, PhS, PhS(O), and 2C5H4N, respectively) with high diastereo-selectivities. Similar reactions of (η6-arene)Ru(DMPP)Cl2 with NaPF6 and allyldiphenyl-phosphine (ADPP) produced the mixed ligand complexes [(η6-arene)Ru(DMPP) (ADPP)Cl2]PF6 which did not undergo subsequent [4+2] Diels–Alder cycloadditions even at elevated temperatures. New complexes were characterized by elemental analyses, physical

  配合物（η 6 -arene）的Ru（DMPP）氯2（DMPP = 3,4-二甲基-1- phenylphosphole;芳烃= C 6 H ^ 6，的MeC 6 ħ 5，p -MeC 6 ħ 4 CHME 2，和C 6 Me 6）与NaPF 6和亲二烯体配体反应：Ph 2 PCH = CH 2（DPVP），Me 2 NC（O）CH = CH 2（DMAA），MeC（O）CH = CH 2（MVK），PhSCH CH 2（PVS），PHS（O）CHCH 2（PVSO），和2-乙烯基吡啶（2VP），以产生[（η 6-arene）的Ru（顺式-外-2- ř -5,6-二甲基-7-苯基-7-磷杂二环[2.2.1]庚-5-烯）CL] PF 6种复合物（R =PPh 2， C（O）NME 2，C（O）Me中，PhS，PhS（O），和2C 5 ħ 4 N，分别地）具有高非对映选择性。的类似反应（η
• Carebene and isocyanide ligation at ruthenium(II) with (η6-arene) and tethered phosphinopropylarene ligands
  作者：Kesete Y Ghebreyessus、John H Nelson

  DOI：10.1016/s0020-1693(02)01492-5

  日期：2003.7

  Reactions of [(eta(6)-1 2,4,5-Me40C6H2)Ru(DPVP)Cl-2] (DPVP = diphenylvinyl phosphine), with (trimethylsilyl)acetylene and phenylacetylene in the presence of NaPF6 in methanol gave the (methoxy)-alkylcarbene complexes [(eta(6)-1,2,4,5-Me4C6H2)Ru(=C (OMe)(R))(DPVP)(Cl)]PF6 (R = CH3, 1a; CH2Ph, 2a). Similarly, treatment of [(eta(6)-1 2,4-Me3C6H2-5-CH2CH2CH2P(C6H5)(2))RuCl2] with (trimethylsilyl) acetylene, phenylacetylene and 1,1-diphenylpropargyl alcohol in the presence of NaPF6 gave the tethered carbene complexes [(eta(6)-1 2,4-Me3C6H2-5-CH2CH2CH2P(C6H5)(2))Ru(=C(OMe)(R))(Cl)PF6 (R = CH3, 1b; CH2Ph, 2b; CH=C-Ph-2, 3b), respectively. The complexes, [(eta(6)-arene)Ru(DPVP)Cl-2] and [(eta(6)-arene-CH2CH2CH2P(C6H5)(2))RuCl2] are shown to be useful catalyst precursors for the hydration of phenylacetylene to afford acetophenone. The complexes, [(eta(6)-arene)Ru(DPVP)Cl-2] (arene = 1,3,5-Me3C6H3 1, p -MeC6H4CHMe2 2, 1,2,4,5-Me4C6H2 3 and Me6C6 4) react with excess phenyl-isocyanide and NaPF6 in methanol to produce [(eta(6)-arene)Ru(DPVP)(CNPh)(Cl)]PF6 derivatives 1c-4c. The related tethered complexes Id and 2d were prepared from [(eta(6)-arene-CH2CH2CH2P(C6H5)(2))RuCl2] by using the same methodology. All the complexes have been characterized spectroscopically and the crystal structures of some of them have been obtained. (C) 2002 Elsevier Science B.V. All rights reserved.
• (η⁶‐Arene)ruthenium(II) Complexes with Hemilabile η³‐Dicyclohexylvinylphosphine (DCVP) and η³‐Diphenylvinylphosphine (DPVP) Phosphaallyl Ligands: Formation of an Unexpected Trinuclear Complex
  作者：John H. Nelson、Kesete Y. Ghebreyessus

  DOI：10.1081/sim-120024313

  日期：2003.1.10

  The complexes [(eta(6)-arene)RuCl2(Cy2PCH=CH2)], [arene=MeC6H5, (1a); p-MeC6H4Me; (2a); p-MeC6H4CHMe2 (3a); 1,2,4,5-Me4C6H2, (4a); and C6Me6, (5a)], have been synthesized by reacting [(eta(6)-arene)RuCl2](2) with dicyclohexylvinylphosphine (DCVP). In the presence of AgPF6, in a 1: 1 dichloromethane/acetone solvent mixture the compound [(eta(6)-C6Me6)RuCl2(Cy2PCH=CH2)] (5a) afforded [(eta(6)-C6Me6)RuCl(eta(3)-DCVP)]PF6 (1b). A similar reaction was conducted with [(eta(6)-C6Me6)RuCl2(Ph2PCH=CH2)] in an attempt to form [(eta(6)-C6Me6)RuCl(eta(3)-DPVP)]PF6 (2b). However, this reaction yielded, instead, the unexpected trinuclear heterobimetallic complex [(eta(6)-C-6-Me-6)Ru(mu-Cl)(2)(Ph2PCH=CH2)}(2)Ag](PF6) (3b) the structure of which was determined by X-ray crystallography. Compound (1b) reacts with phenylisocyanide to form [(eta(6)-C6Me6)RuCl(eta(1)-DCVP)(CNPh)]PF6. The complexes have been characterized by H-1, P-31H-1} and C-13(H-1) NMR spectroscopy, elemental analyses, cyclic voltammetry, and in some cases [compounds (4a), (1b) and (3b)] by X-ray crystallography.
• Reactions of [(η6-Me6C6)Ru(Ph2PCHCH2)Cl2] with 1-ethynylcycloalkanols leading to methoxy-alkenyl carbenes via vinylvinylidene and/or allenylidene intermediates
  作者：Kesete Y. Ghebreyessus、John H. Nelson

  DOI：10.1016/s1387-7003(03)00177-1

  日期：2003.8

  Methoxy-alkenyl carbenes 1 and 2 have been synthesized by treating a dichloro-methane/methanol solution of the [(eta(6)-Me6C6)Ru(Ph2PCH=CH2)Cl-2] complex with an excess of I-ethynyl-l-cyclohexanol and I-ethynyl-l-cyclopentanol in the presence of NaPF6. The compounds were characterized by IR and H-1, C-13H-1}, P-31H-1} NMR spectroscopies and by elemental analyses. The crystal structure of 2 has also been determined by X-ray crystallography. (C) 2003 Elsevier Science B.V. All rights reserved.
• Novel Ruthenium(II) Carbene Complexes:  Products of the Reactions of 1-Alkynes with (η⁶-C₆Me₆)Cl₂Ru(PR₃)
  作者：Heather D. Hansen、John H. Nelson

  DOI：10.1021/om0004949

  日期：2000.11.1

  The complexes (eta6-C6Me6)Cl2RU(PR3) (1; PR3 = DPVP (diphenylvinylphosphine) (a), PMe3 (b), PPh3 (c)) react with NaPF6 in acetonitrile solutions to give the cationic complexes [(eta (6)-C6Me6)ClRu(PR3)(NCCH3)]PF6 (2a-c) by loss of NaCl, Complexes la and 2a react with HC=CSiMe3 and HC=CPh land NaPF6 for 1a) in MeOH to give the carbene complexes [(eta (6)-C6Me6)Cl(DPVP)Ru=C (OCH3)CH3]PF6 (3a) and [(eta (6)-C6Me6) Cl(DPVP)Ru=C(OCH3)CH2Ph]PF6 (4a), respectively. The known analogues 3b,c and 4b and the new complex 4c have been synthesized from 2b,c and HC drop CR. The solid-state structures of these complexes show a wide variation in the orientation of the carbene plane with respect to the plane of the eta (6)-arene ring (dihedral angles of 37,9-59,6 degrees) The solution dynamic behavior of 3a-c and 4a-c is discussed, Complex 2a also reacts with HC drop CCH2CH2OH in MeOH to give the oxacyclic carbene complex [(eta (6)-C6Me6)Cl(DPVP)Ru=C(CH2CH2CH2)O]PF6 (5). 1a (and NaPF6) and 2a react with HC=CC(OH)Ph-2 in MeOH to give the novel phosphorus ylide complex [(eta (6)-C6Me6)ClRuC(=C=CPh2)PPh2CH=CH2]PF6 (6) and with dimethylpropargylamine in CH2Cl2 or dichloroethane to give the amino cyclic carbene complex [(eta (6)- C6Me6)Cl(DPVP)Ru= CCH2- CMe2NH]PFG (7) and the metallacyclic complex [(r76-CsMes)C1RuCH=C(DPVP)CMe2NH21PFB (8). In the absence of MeOH, reaction of 2a with HC=CC(OH)Ph-2 gives the dimeric complex [(eta (6)-C6Me6)Ru(mu -Cl)(3)Ru(eta (6)-C6Me6)]PF6. Complex 2a plus HC=CPh in the absence of MeOH gives the carbonyl complex [(eta (6)-C6Me6)Cl(DPVP)Ru(CO)]PF6 (9), Reaction of 2c with HC=CPh in MeOH for extended time periods (>1 day) gives an analogous carbonyl complex of PPh3, [(eta (6)-C6Me6)Cl(PPh3)Ru(CO)]PF6. All complexes have been characterized by H-1, C-131H}, and P-31H-1} NMR and IR spectroscopies and electrochemistry and in most cases by X-ray crystallography. Complex la is an efficient catalyst for the regioselective addition of H2O to HC=CPh, producing exclusively acetophenone in 70% isolated yield.