Ru2(CO)(μ-CO)(μ-η1,η3-C(C(CH3)2OH)CHCH2)(η-C5H5)2 | 676255-18-8

• 英文名称: Ru2(CO)(μ-CO)(μ-η1,η3-C(C(CH3)2OH)CHCH2)(η-C5H5)2
• CAS: 676255-18-8
• 化学式: C₁₈H₂₀O₃Ru₂
• 分子量: 486.495
• InChiKey: LIAJBAMRTDYWIM-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  tetrafluoroboric acid 、 Ru2(CO)(μ-CO)(μ-η1,η3-C(C(CH3)2OH)CHCH2)(η-C5H5)2 以 四氢呋喃 为溶剂， 以90%的产率得到[Ru2(CO)(μ-CO)(μ-η2,η3-(C(methyl)2CCHCH2)(η-C5H5)2](BF4)
  参考文献：
  名称：

  Synthesis and reactivity of μ-butadienyl diruthenium cations

  摘要：

  Propargyl alcohols HC-CCR2OH (R = H, Me or Ph) react with [Ru-2(CO)(MeCN)(mu-CO)(mu-CH2)(eta-C5H5)(2)] (2) to form the allylidene complexes [Ru-2(CO)(mu-CO) {mu-eta(1), eta(3)-C(CR2OH)CH=CH2} (q-C5H5)(2)] (4a, R = H; 4b, R = Me; 4c, R = Ph). Treatment of complexes 4a-c with HBF4 removes the hydroxide group as water, giving the 2-butadienyl complexes [Ru-2(CO)(mu-CO)(mu-eta(2), eta(3)- CR2=CCH=CH2)(eta-C5H5)(2)][BF4] (5a, R = H; 5b, R = Me; 5c, R = Ph). The reactivity of 5a-c towards nucleophiles and bases is described. With hydride, 5a-c undergo nucleophilic attack at the C(R,) carbon to give the allylidene complexes [Ru-2(CO)(mu-CO){mu-eta(1), eta(3)-C(CR2H)CH=CH2}(eta-C5H5)(2)] (6a, R=H; 7, R=Me; 11, R=Ph) and, in the case of 5c, the butadiene complex [Ru-2(CO)(2)(mu-eta(2), eta(2)-CPh2=CHCH=CH2)(eta-C5H5)(2)] (12) and the allene complex [Ru-2(CO)(2)(mu-eta(2), eta(2)-CPh2=C=CHMe)(eta-C5H5)(2)] (13), formally due to attack at the p-C and CH, carbons, respectively. The complexes 5a-c react with methyl lithium to undergo nucleophilic attack predominantly at the C(R-2) carbon, giving methylated allylidene complexes [Ru-2(CO)(mu-CO){mu-eta(1), eta(3)-C(CR2Me)CH=CH2}(eta-C5H5)(2)] (6b, R=Me; 9, R=Me; 14, R=Ph). With 5b and 5c methyl lithium also acts as a base, abstracting protons to give the novel divinylcarbene complex [Ru-2(CO)(mu-CO) {mu-eta(1), eta3-C(CMe=CH2)CH=CH2}(eta-C5H5)(2)] (8) and the mu-butatriene complex [Ru-2(CO)(2)(mu-eta(2), eta(2)-CPh2=C=C=CH2)(eta-C5H5)(2)] (15), respectively. Complexes 8 and 15 are formed exclusively by treating 5b and 5c, respectively, with diazabicyclo[5.4.0]undec-7-ene (DBU). Complexes 8 and 9 were also prepared in good yield by reaction of complex 2 with 2-methyl-1-buten-3-yne {CH2=C(Me)Cequivalent toCH} and t-butylacetylene, respectively. Treatment of complex 8 with HBF4 resulted in protonation at each of the methylene groups, affording 5b and isomeric [Ru-2(CO)(mu-CO) {mu-eta(2), eta(3)-CH(Me)=CC(Me)=CH2}(eta-C5H5)(2)][BF4] (10). The structures of 5b, 5c and 8 were established by X-ray diffraction. (C) 2003 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(03)00391-8
• 作为产物：
  描述：

  Ru2(CO)(acetonitrile)(μ-CO)(μ-CH2)(η-C5H5)2 、 2-甲基-3-丁炔-2-醇 以 二氯甲烷 、 乙腈 为溶剂， 生成 Ru2(CO)(μ-CO)(μ-η1,η3-C(C(CH3)2OH)CHCH2)(η-C5H5)2
  参考文献：
  名称：

  Synthesis and reactivity of μ-butadienyl diruthenium cations

  摘要：

  Propargyl alcohols HC-CCR2OH (R = H, Me or Ph) react with [Ru-2(CO)(MeCN)(mu-CO)(mu-CH2)(eta-C5H5)(2)] (2) to form the allylidene complexes [Ru-2(CO)(mu-CO) {mu-eta(1), eta(3)-C(CR2OH)CH=CH2} (q-C5H5)(2)] (4a, R = H; 4b, R = Me; 4c, R = Ph). Treatment of complexes 4a-c with HBF4 removes the hydroxide group as water, giving the 2-butadienyl complexes [Ru-2(CO)(mu-CO)(mu-eta(2), eta(3)- CR2=CCH=CH2)(eta-C5H5)(2)][BF4] (5a, R = H; 5b, R = Me; 5c, R = Ph). The reactivity of 5a-c towards nucleophiles and bases is described. With hydride, 5a-c undergo nucleophilic attack at the C(R,) carbon to give the allylidene complexes [Ru-2(CO)(mu-CO){mu-eta(1), eta(3)-C(CR2H)CH=CH2}(eta-C5H5)(2)] (6a, R=H; 7, R=Me; 11, R=Ph) and, in the case of 5c, the butadiene complex [Ru-2(CO)(2)(mu-eta(2), eta(2)-CPh2=CHCH=CH2)(eta-C5H5)(2)] (12) and the allene complex [Ru-2(CO)(2)(mu-eta(2), eta(2)-CPh2=C=CHMe)(eta-C5H5)(2)] (13), formally due to attack at the p-C and CH, carbons, respectively. The complexes 5a-c react with methyl lithium to undergo nucleophilic attack predominantly at the C(R-2) carbon, giving methylated allylidene complexes [Ru-2(CO)(mu-CO){mu-eta(1), eta(3)-C(CR2Me)CH=CH2}(eta-C5H5)(2)] (6b, R=Me; 9, R=Me; 14, R=Ph). With 5b and 5c methyl lithium also acts as a base, abstracting protons to give the novel divinylcarbene complex [Ru-2(CO)(mu-CO) {mu-eta(1), eta3-C(CMe=CH2)CH=CH2}(eta-C5H5)(2)] (8) and the mu-butatriene complex [Ru-2(CO)(2)(mu-eta(2), eta(2)-CPh2=C=C=CH2)(eta-C5H5)(2)] (15), respectively. Complexes 8 and 15 are formed exclusively by treating 5b and 5c, respectively, with diazabicyclo[5.4.0]undec-7-ene (DBU). Complexes 8 and 9 were also prepared in good yield by reaction of complex 2 with 2-methyl-1-buten-3-yne {CH2=C(Me)Cequivalent toCH} and t-butylacetylene, respectively. Treatment of complex 8 with HBF4 resulted in protonation at each of the methylene groups, affording 5b and isomeric [Ru-2(CO)(mu-CO) {mu-eta(2), eta(3)-CH(Me)=CC(Me)=CH2}(eta-C5H5)(2)][BF4] (10). The structures of 5b, 5c and 8 were established by X-ray diffraction. (C) 2003 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(03)00391-8