cis-((η5-C5H3)2(CMe2)2)Ru2(CO)4Br2 | 1242067-97-5

• 英文名称: cis-((η5-C5H3)2(CMe2)2)Ru2(CO)4Br2
• 英文别名: cis-((η5-5H3)2(CMe2)2)Ru2(CO)4Br2
• CAS: 1242067-97-5
• 化学式: C₂₀H₁₈Br₂O₄Ru₂
• 分子量: 684.309
• InChiKey: VKMTZADDSYXDNL-UHFFFAOYSA-L

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

• 作为反应物：
  描述：

  cis-((η5-C5H3)2(CMe2)2)Ru2(CO)4Br2 、 silver trifluoromethanesulfonate 以 二氯甲烷 为溶剂， 以92%的产率得到[cis-((η5-C5H3)2(CMe2)2)Ru2(CO)4(μ-Br)]OTf
  参考文献：
  名称：

  Syntheses and Characterization of Ruthenium Complexes Containing a Doubly Linked Dicyclopentadienyl Ligand and Acetonitrile Ligands

  摘要：

  The reaction of a mixture of isomers of 4,4,8,8-tetramethyl-tetrahydro-s-indacene (1) with Ru(3)-(CO)(12) afforded cis-{(eta(5)-C(5)H(3))(2)(CMe(2))(2)}Ru(2)(CO)(4), (2) in 68% yield. Reaction of 2 with Br(2) gave cis-{(eta(5)-C(5)H(3))(2)(CMe(2))(2)}Ru(2)(CO)(4)Br(2) (3) in 88% yield. Reaction of 3 with AgOTf yields cis-[{(eta(5)-C(5)H(3))(2)(CMe(2))(2)}Ru(2)(CO)(4)(mu-Br)][OTf] (4), while reaction of 3 with Me(3)NO and AgOTf yields cis-[{(eta(5)-C(5)H(3))(2)(CMe(2))(2)}Ru(2)(CO)(2)(MeCN)(2)(mu-Br)][OTf] (5). Reaction of 3 under more forcing conditions with AgOTf in MeCN gave cis-[{(eta(5)-C(5)H(3))(2)(CMe(2))(2)}Ru(2)(CO)(2)(MeCN)(4)][OTf](2) (6), while a MeCN/C(6)H(6) solvent combination afforded cis-[{(eta(5)-C(5)H(3))(2)(CMe(2))(2)}Ru(2)(eta(6)-C(6)H(6))(2)][OTf](2) (7) in a 64% yield. Removal of the benzene ligands in 7 can be accomplished by first adding H(-) to the coordinated benzene ligands to afford cis-{(eta(5)-C(5)H(3))(2)(CMe(2))(2)}Ru(2)(eta(5)-C(6)H(7))(2) (10). Subsequent protonation of 10 in MeCN afforded [cis-{(eta(5)-C(5)H(3))(2)(CMe(2))(2)}Ru(2)(MeCN)(6)][OTf](2) (8) in 88% yield. Structural data for 4, 5, 7, and 10 are reported.

  DOI：

  10.1021/om100566w
• 作为产物：
  描述：

  cis-((η5-C5H3)2(CMe2)2)Ru2(CO)4 、 溴 以 二氯甲烷 为溶剂， 以88%的产率得到cis-((η5-C5H3)2(CMe2)2)Ru2(CO)4Br2
  参考文献：
  名称：

  Syntheses and Characterization of Ruthenium Complexes Containing a Doubly Linked Dicyclopentadienyl Ligand and Acetonitrile Ligands

  摘要：

  The reaction of a mixture of isomers of 4,4,8,8-tetramethyl-tetrahydro-s-indacene (1) with Ru(3)-(CO)(12) afforded cis-{(eta(5)-C(5)H(3))(2)(CMe(2))(2)}Ru(2)(CO)(4), (2) in 68% yield. Reaction of 2 with Br(2) gave cis-{(eta(5)-C(5)H(3))(2)(CMe(2))(2)}Ru(2)(CO)(4)Br(2) (3) in 88% yield. Reaction of 3 with AgOTf yields cis-[{(eta(5)-C(5)H(3))(2)(CMe(2))(2)}Ru(2)(CO)(4)(mu-Br)][OTf] (4), while reaction of 3 with Me(3)NO and AgOTf yields cis-[{(eta(5)-C(5)H(3))(2)(CMe(2))(2)}Ru(2)(CO)(2)(MeCN)(2)(mu-Br)][OTf] (5). Reaction of 3 under more forcing conditions with AgOTf in MeCN gave cis-[{(eta(5)-C(5)H(3))(2)(CMe(2))(2)}Ru(2)(CO)(2)(MeCN)(4)][OTf](2) (6), while a MeCN/C(6)H(6) solvent combination afforded cis-[{(eta(5)-C(5)H(3))(2)(CMe(2))(2)}Ru(2)(eta(6)-C(6)H(6))(2)][OTf](2) (7) in a 64% yield. Removal of the benzene ligands in 7 can be accomplished by first adding H(-) to the coordinated benzene ligands to afford cis-{(eta(5)-C(5)H(3))(2)(CMe(2))(2)}Ru(2)(eta(5)-C(6)H(7))(2) (10). Subsequent protonation of 10 in MeCN afforded [cis-{(eta(5)-C(5)H(3))(2)(CMe(2))(2)}Ru(2)(MeCN)(6)][OTf](2) (8) in 88% yield. Structural data for 4, 5, 7, and 10 are reported.

  DOI：

  10.1021/om100566w

文献信息

• Diruthenium Naphthalene and Anthracene Complexes Containing a Doubly Linked Dicyclopentadienyl Ligand
  作者：Hélori Salembier、Joshua Mauldin、Tom Hammond、Rodney Wallace、Essa Alqassab、Michael B. Hall、Lisa M. Pérez、Yuen-Jing Alexis Chen、Katherine E. Turner、Eric Bockoven、William Brennessel、Robert M. Chin

  DOI：10.1021/om300384d

  日期：2012.7.9

  the C2v isomer, which is a transition state. Reaction of cis-(η5-C5H3)2(CMe2)2}Ru2(CO)4Br2 with anthracene affords the analogous syn-facial anthracene complex, [cis-(η5-C5H3)2(CMe2)2}Ru2(μ-η6,η6-C14H10)][OTf]2, (4), and the tetranuclear dianthracene complex, [cis-(η5-C5H3)2(CMe2)2}Ru2(μ-η6,η6-C14H10)]2[OTf]4, (5). 22+, 20, and 5 were structurally characterized by X-ray diffraction.

  的反应顺- （η 5 -C 5 H ^ 3）2（CME 2）2 }的Ru 2（CO）4溴2与萘，得到顺-facial [顺式- （η 5 -C 5 H ^ 3）2（CME 2）2 }的Ru 2（μ-η 6，η 6 -C 10 ħ 8）] [光学传递函数] 2，（2 2+），看来是比18电子定律少两个电子的络合物。密度泛函理论（DFT）的计算表明，Ru原子通过弱金属-金属键和共享来自萘中心π键的电子的组合来满足其缺失价。的单电子还原2个2+产量2 +，一类II混合价复合物，而这两个电子还原2 2+引起从一个η变化哈普托数6至η 4上的萘环和产率的一个顺- （η 5 -C 5 H ^ 3）2（CME 2）2 }的Ru 2（μ-η 6，η 4 -C 10 ħ 8 ）（2 0），两性离子复合物。DFT计算预测2 0的C s异构体的能量比过渡态的C 2 v异构体低4.69 kcal / mol