RuCl2(PMe3)(η6-1,2,4,5-Me4C6H2) | 129127-58-8

• 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: RuCl2(PMe3)(η6-1,2,4,5-Me4C6H2)
• 英文别名: Dichlororuthenium;1,2,4,5-tetramethylbenzene;trimethylphosphane
• CAS: 129127-58-8
• 化学式: C₁₃H₂₃Cl₂PRu
• 分子量: 382.275
• InChiKey: DXWWFCDASBFANA-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  5.65
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.54
• 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：

  RuCl2(PMe3)(η6-1,2,4,5-Me4C6H2) 、 2-甲基丁-3-炔-1-醇 在 NaPF₆ 、 but-3-en-1-ol 作用下， 以 neat (no solvent) 为溶剂， 以48%的产率得到
  参考文献：
  名称：

  One-step synthesis of alkenyloxy–alkenylcarbene complexes and the unprecedented formation of an η⁵-allyl-alkene ruthenium complex

  摘要：

  四甲基苯烯氧基烯基羰基钌(II)衍生物[(C6Me4H2)Ru{C[O(CH2)mCHCH2]CHCHâ(CHCH)n-R}Cl(PMe3)]PF6(m= 1,2；n=0、1、2)在丙炔醇衍生物 HCCâC(H)(OH)[(CHCH)n-R] 和乙烯醇的存在下通过 (C6Me4H2)RuCl2(PMe3) 一步反应生成，而与 HCCâC(OH)Me2 的类似反应则生成了一种新型的 Î-5- 烯丙基烯烃钌配合物，并通过 X 射线晶体结构分析对其进行了表征。

  DOI：

  10.1039/c39920001220

文献信息

• Vinylacetylene (butenyne) derivatives as precursors of alkenylcarbene ruthenium complexes via allenylidene metal intermediates
  作者：Dominique Devanne、Pierre H. Dixneuf

  DOI：10.1039/c39900000641

  日期：——

  Complexes (η6-arene)(PR3)RuCl2(1a—c) react with HCC–C(R1)CHR2 derivatives in methanol to afford in one step the alkenylcarbene–ruthenium cations [(η6-arena)(PR3)ClRuC(OMe)CHC(R1)CH2R2]+(2)–(6)(R1 and R2= H or Me) which on deprotonation give cyclometallacarbenes (7)–(8); on the basis of labelling experiments the formation of (2)–(6) involves an allenylidene intermediate RuCCC(R1)(CH2R2)+ instead of

  络合物（η 6 -arene）（PR 3）的RuCl 2（1A - C ^）与反应HC C-C（R 1）CHR 2个的甲醇衍生物在一个步骤中，得到alkenylcarbene -钌阳离子[（η 6 -arena） （PR 3）ClRu C（OMe）CH C（R 1）CH 2 R 2 ] +（2）–（6）（R 1和R 2 = H或Me），在去质子化后得到环金属碳烯（7）–（8）; 根据标记实验，（2）–（6）的形成涉及亚烯基中间体Ru C C C（R 1）（CH 2 R 2）+，而不是预期的烯丙基碳烯基团Ru C（OMe）CH 2 C（ R 1）（CHR 2）+。
• Functionalised alkenylcarbene metal complexes (M=Ru, W, Cr) by activation of propargyl alcohol derivatives
  作者：Karine Ulrich、Emmanuel Porhiel、Vincent Péron、Vincent Ferrand、Hubert Le Bozec

  DOI：10.1016/s0022-328x(00)00038-3

  日期：2000.4

  [Ru(η5-C5H5)(CO)(PPh3)(C(OMe)(CHCH-p-C6H4X)][BF4] (4a and 4d) are obtained from [Ru(η5-C5H5)(CO)(PPh3)(Cl)] (3) and propargyl alcohol derivatives a and d, respectively. Treatment of M(CO)5(THF) (M=W, Cr) with a and HCC(H)(OH)C4H2S(OH)(H)CCH (b) yields the monometallic complexes (CO)5MC(OMe)(C(OMe)(CHCHAr(OH)(H)CCH)] (5a) (M=W; Ar=C6H4), 5b (M=W; Ar=C4H2S), and 7a (M=Cr; Ar=C6H4)

  芳烃钌的反应（II）配合物的[Ru（η 6 -C 6我4 - [R 2）（PME 3）氯2 ]（1，R =甲基; 1 '，R = H）与炔丙醇衍生物HCC （H）（OH）（p -C 6 H ^ 4 X）（一个，X =HCC（H）（OH）; C ^，X = CHO; d，X =CHCH 2 ; ê，X = CHCHCHCH 2）和甲醇给出（甲氧基）-alkenylcarbene钌络合物的[Ru（η 6 -C 6我4 - [R 2）（PME3）（CL）（C（OME）（CHCH- p -C 6 H ^ 4 X）] [PF 6 ]（2A）和（2 ' ç - ë）。类似地，半夹心卡宾络合物的[Ru（η 5 -C 5 H ^ 5）（CO）（PPH 3）（C（OME）（CHCH- p -C 6 H ^ 4 X）] [BF 4 ]（图4a和4d中获得）从的[Ru（η 5 -C 5
• Novel behaviour of dialkylamino-substituted propargylic alcohols in reactions with arene ruthenium(II) complexes
  作者：Didier Pilette、Samuel Moreau、Hubert Le Bozec、Pierre H. Dixneuf、John F. Corrigan、Arthur J. Carty

  DOI：10.1039/c39940000409

  日期：——

  Reaction of arene ruthenium(II) derivatives (C6Me4R2)RuCl2(L)(R = H, Me; L = PMe3, PPh3) with the prop-2-ynylic alcohol derivative HCC–C(H)(OH)(C6H4-p-NMe2) in dichloromethane results in the formation of new oxametallacyclic ruthenium(II) complexes (C6Me4R2)Ru[CHC(C6H4-p-NMe2)CHO](L)} PF6via an unprecedented 1,2-migration of the dimethylaminophenyl substituent; the structure of one compound (R = H; L = PPh3) is determined by an X-ray crystal structure analysis.

  在二氯甲烷中，芴钌(II)衍生物 (C6Me4R2)RuCl2(L)(R = H，Me；L=PMe3、PPh3）与丙-2-炔醇衍生物 HCC-C(H)(OH)(C6H4-p-NMe2)在二氯甲烷中反应，通过二甲氨基苯基取代基前所未有的 1,2 迁移，形成了新的氧杂环钌(II)配合物 (C6Me4R2)Ru[CHC(C6H4-p-NMe2)CHO](L)} PF6；通过 X 射线晶体结构分析确定了一种化合物（R = H；L = PPh3）的结构。
• Activation of 2-propyn-1-ol derivatives by (arene)ruthenium(II) complexes: new route to (alkenylcarbene)- and (polyenylcarbene)-metal complexes
  作者：Didier Pilette、Khalid Ouzzine、Hubert Le Bozec、Pierre H. Dixneuf、Clifton E. F. Rickard、Warren R. Roper

  DOI：10.1021/om00038a046

  日期：1992.2

  Reactions of the (arene)ruthenium(II) complexes (eta(6)-arene)(PMe3)RuCl2 (arene = C6Me6 (1), C6Me4H2 (1')) with disubstituted HC = CC(R)(R')OH (R,R' = Me, Me (a), cyclohexyl (b), Ph, Ph (c)) or mono-substituted 2-propyn-1-ols HC = CC(R)(H)OH (R = Me (d), Ph (e), 2-thienyl (f)), in methanol containing NaPF6, lead to the cationic methoxyalkenylcarbene complexes [(eta(6)-arene)(PMe3)(Cl)Ru = C(OMe)(CH = CRR')]PF6 (2,2',R' not-equal H; 3, 3', R' = H) in ca. 70% yield. Difference H-1 NOE experiments establish an s-cis conformation for ((monosubstituted alkenyl)carbene)ruthenium moieties (3, 3') and an s-trans conformation in (disubstituted alkenyl)carbene complexes 2 and 2'. A crystal structure of [(eta(6)-C6Me6)-(PMe3)(Cl)Ru = C(OMe)(CH = CPh2)]PF6 (2c) has been determined by X-ray diffraction. It shows an s-trans conformation for the methoxy(diphenylalkenyl)carbene moiety. Crystal data are as follows: monoclinic, P2(1)/n, with a = 9.826 (2) angstrom, b = 15.659 (1) angstrom, c = 21.552 (2) angstrom, beta = 92.89 (1)-degrees, V = 3312.0 (6) angstrom 3, Z = 4, R = 6.9%, R(w) = 7.2%. Treatments of 1 and 1' with HC = CC(CH = CHR)(H)OH (R = Ph (g), Me (h)) and HC = CC(CH = CHCH = CHMe)(H)OH (i) produce dienylcarbene (4g,4'h) and trienylcarbene (5i, 5'i) ruthenium complexes in 70-90% yield. Reaction of 1 with HC = CCH2OH in methanol gives a double addition of MeOH and generates [(eta(6)-C6Me6)(PMe3)(Cl)Ru = C(OMe)(CH2CH2OMe)]PF6 (7). Methoxyalkenylcarbene complexes 2-5 and 2'-5' are formed via allenylidene intermediates [(eta(6)-C6Me6)(L)(Cl)-Ru = C = C = CPh2]PF6 that have been trapped during the reaction of (eta(6)-C6Me6)(L)RuCl2 (L = PMe3 (1), PPh3 (8)) with HC = CCPh2OH (c) in methanol (9c, 10c). The (allenylidene)ruthenium intermediate can be stabilized by the introduction of a ferrocenyl group at C3: reaction between HC = CC(Ph)(Fc)OH (j) and 1 in methanol only leads to the stable complex [(eta(6)-C6Me6)(PMe3)(Cl)Ru = C = C = C(Ph)(Fc)]PF6 (11j).
• Carbene derivatives of areneruthenium(II) complexes in one step from terminal alkynes
  作者：Dominique Devanne、Pierre H. Dixneuf

  DOI：10.1016/0022-328x(90)85105-8

  日期：1990.7