(cyclopentadienyl)Ru(η(1)-O2CCF3)(PPh3)2 | 198084-34-3

• 英文名称: (cyclopentadienyl)Ru(η(1)-O2CCF3)(PPh3)2
• 英文别名: CpRu(OC(O)CF3)(PPh3)2；RuCp(PPh3)2(CF3CO2)
• CAS: 198084-34-3
• 化学式: C₄₃H₃₅F₃O₂P₂Ru
• 分子量: 803.762
• InChiKey: HUKCERHNFMXCFA-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  (cyclopentadienyl)Ru(η(2)-O2CCF3)(PPh3) 、 三苯基膦 以 甲苯 为溶剂， 以70%的产率得到(cyclopentadienyl)Ru(η(1)-O2CCF3)(PPh3)2
  参考文献：
  名称：

  Cyclopentadienyl— und Pentamethylcyclopentadienyl—Rutheniumkomplexe mit Carboxylat-, Vinylester- und Carben-Liganden

  摘要：

  Monomeric carboxylatoruthenium(II) complexes [C5R5Ru(eta(2)-O2CR')(PPh3)] (R = H, Me; R' = Me, Bu-t, CF3) were prepared by ligand displacement from [(C5R5)Ru(eta(3)-2-MeC3H4)(PPh3)] and R'CO2H. From a similar route, the tosylato and pentachlorphenolato derivatives [C5H5Ru{O2SO(p-C6H4Me)}(PPh3)](n) and [C5H5Ru(eta(2)-OC6Cl5)(PPh3)] were obtained. On treatment with PhNH2, CO, PPh3 and O-2, they reacted to give the complexes [C5H5Ru{O2SO(p-C6H4Me)}(L)(PPh3)] and [C5H5Ru(OC6Cl5(CO)(PPh3)] respectively. The reaction of [C5R5Ru(eta(2)-O2CRt)(PPh3)] (R' = Me, Bu-t) with terminal alkynes HC=CR (R = CO2Me, Ph) yielded the vinylesterruthenium(II) compounds [C5H5Ru(kappa(2)(C,O)-C(=CHR)OC(R')=O}(PPh3)] for which a resonance structure involving a carboxylato(vinylidene) species is postulated. The carbene half-sandwich type complexes [C5H5RuCl(=CRR')(PPh3)] (R and R' = C6H4X) were prepared in two steps from [C5H5Ru(eta(2)-O2CMe)(PPh3)], N2CRR' and either Al2O3/Cl- or Et3NHCl. The molecular structure of [C5Me5Ru(eta(2)-(O2CBu)-Bu-t)(PPh3)] and [C5H5RuCl(=CPh2)(PPh3)] have been determined by X-ray single-crystal structural investigations.

  DOI：

  10.1016/s0022-328x(97)00045-4

文献信息

• Acid-Promoted sp³ C–H Bond Cleavage in a Series of (2-Allylphenoxo)ruthenium(II) Complexes. Mechanistic Insight into the Aryloxo–Acid Interaction and Bond Cleavage Reaction
  作者：Masafumi Hirano、Masahiro Murakami、Toshinori Kuga、Nobuyuki Komine、Sanshiro Komiya

  DOI：10.1021/om200974c

  日期：2012.1.9

  interaction. Interestingly, further association of 2·HOR with the second acid leads to the cleavage of the benzylic C–H bond, giving RuCp[C3H41-C6H3(OH-2)(R)}-η3C,C′,C″](PPh3) (3). The thermodynamic and kinetic studies suggest formation of hydrogen bonds among two Brϕnsted acid molecules, lone-pair electrons in the aryloxo oxygen, and a benzylic methylene proton. Such association makes the Ru(II) center more

  一系列RuCp的[OC 6 H ^ 3（CH 2 CH = CH 2 -2）（R）]（PPH 3）ñ络合物（Ñ = 2，R = H（1A）; ñ = 1，R = 4-OME （2b），4-Me（2c），4-Ph（2d），4-Br（2e），4-NO 2（2f），6-OMe（2g），6-Me（2h），6-Ph （2i））的收率为27–76％。这些2-烯丙基芳基氧配合物1a和2b – f在RuCp [OC之间处于平衡状态6 ħ 3（CH 2 CH = CH 2 -2）（R）-κ 1 ö ]（PPH 3）2（1）和RuCp [OC 6 H ^ 3（CH 2 CH = CH 2 -2）（R） - κ 1 Ò，η 2 ç，ç ']（PPH 3）（2在溶液中），和2克-我不与反应PPH 3。平衡常数K 1（K 1 = [ 2 ] [PPh 3] / [ 1 ]）对于1a和2b – f大约相同（K 1 =
• Reactions of Furylruthenium Complexes with Oxygen and Trimethylsilyl Azide
  作者：Ku‐Hsien Chang、Hui‐Ling Sung、Ying‐Chih Lin

  DOI：10.1002/ejic.200500621

  日期：2006.2

  The reaction of the (α-alkoxyfuryl)ruthenium complexes 4 with oxygen opens the five-membered furyl ring to give the addition product [Ru]O2CCR=CHCO2CH3, (5, [Ru] = Cp(PPh3)2Ru). Further reactions of 5 with CH3I and with organic acid gave CH3O2CCR=CHCO2CH3, (6), and HO2CCR=CHCO2CH3, (7), respectively. The reaction of 4 with TMSN3 [TMS = (CH3)3Si] gives the ruthenium azide [Ru]–N3 and α-alkoxyfuran,

  (α-烷氧基呋喃基)钌配合物4与氧的反应打开了五元呋喃环，得到加成产物[Ru]O2CCR=CHCO2 ，(5，[Ru]=Cp(PPh3)2Ru)。5 与 CH3I 和有机酸的进一步反应分别得到 O2CCR=CHCO2 ，（6）和 HO2CCR=CHCO2 ，（7）。4 与 TMSN3 [TMS = (CH3)3Si] 反应生成叠氮化钌 [Ru]-N3 和 α-烷氧基呋喃，它们在酸性介质中很容易水解成内酯。用 TMSN3 处理含有巴豆酸甲酯基团的环丙烯基钌配合物 11b 得到五元环三唑和 [Ru]-CN。在该反应中，三元环的 C=C 双键断裂可能是由于 TMSN3 连续添加到反应过程中形成的中间体的烯烃碳原子上。（© Wiley-VCH Verlag GmbH & Co. KGaA，
• Organometallic Ruthenium Complexes:  Application in the Olefination of Carbonyl Compounds
  作者：Filipe M. Pedro、Ana M. Santos、Walter Baratta、Fritz E. Kühn

  DOI：10.1021/om060508w

  日期：2007.1.1

  Ruthenium compounds of general formula Cp‘RuX(PR2R‘)2 (Cp‘ = η5-C5H5 (Cp), η5-C9H7 (Ind), η5-C5(CH3)5 (Cp*); X = Cl, CF3C(O)O; R = C6H5 (Ph), C6H4(CH3) (m-tolyl); R‘ = C6H5, C6H11 (Cy), C6H4(CH3) (m-tolyl, o-tolyl)) are examined as catalysts for the aldehyde olefination starting from diazo compounds, phosphanes, and aldehydes. Cp*RuCl(PPh3)2 is highly active for the olefination of several aldehydes

  通式CP'RuX（PR的钌化合物2 R '）2（CP'=η 5 -C 5 H ^ 5（CP），η 5 -C 9 ħ 7（茚基），η 5 -C 5（CH 3）5（CP *）; X =氯，CF 3 C（O）O; R = C 6 H ^ 5（PH），C 6 H ^ 4（CH 3）（米-甲苯基）; R” = C 6 H ^ 5， C 6 H 11（Cy），C 6 H 4（CH3）（米-甲苯基，ö甲苯基））被检查作为催化剂用于醛烯从重氮化合物，膦，和醛开始。CP * RuCl（PPh 3）2对几种醛的烯化反应具有很高的活性，表现出非常高的E选择性，以及对酮的烯化反应（以苯甲酸为助催化剂）。通过分离催化活性反应物种，即卡宾/膦钌混合配合物CP * RuCl（CHCO 2 Et）（PPh 3）（8），可以证实该反应的机理。光谱研究表明，后者与PPh 3反应生成磷酰化磷Ph 3 P CHCO 2 Et，该磷酰化磷进一步与醛反应生成烯烃。