cis-((η5-C5H3)2(CMe2)2)Ru2(CO)4 | 1242067-96-4

• 英文名称: cis-((η5-C5H3)2(CMe2)2)Ru2(CO)4
• CAS: 1242067-96-4
• 化学式: C₂₀H₁₈O₄Ru₂
• 分子量: 524.501
• InChiKey: QEECRAIWLJORSC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
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• 环数：
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• 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)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
• 作为产物：
  描述：

  十二羰基三钌 、 4,4,8,8-tetramethyl-1,4,5,8-tetrahydro-s-indacene 、 4,4,8,8-tetramethyl-1,4,5,8-tettahydro-s-indacene 在 1-heptene 作用下， 以 正庚烷 为溶剂， 以68%的产率得到cis-((η5-C5H3)2(CMe2)2)Ru2(CO)4
  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

• Reactivity of Methyl Diruthenium Complexes with CO and Bipyridine Ligands
  作者：Nina J. Bonde、Michael B. Hall、Xin Yang、William W. Brennessel、Nia N. McClendon、Robert M. Chin

  DOI：10.1021/acs.organomet.1c00445

  日期：2021.10.11

  different methyl diruthenium complexes, [cis-(η5-C5H3)2(CMe2)2}Ru2(CO)4(CH3)][OTf] and [cis-(η5-C5H3)2(CMe2)2}Ru2(κ2-(4,4′-di-tert-butyl)-2,2′-bipyridine)2(μ-CH3)][B(ArF)4], have been synthesized and characterized. When CO is the ancillary ligand, the CH3 group is terminal and susceptible to migration to the Cp ligand. Computationally, this methyl complex has two Ru(II) centers with a dative bond

  两种不同的甲基二钌配合物，[ cis- (η 5 -C 5 H 3 ) 2 (CMe 2 ) 2 }Ru 2 (CO) 4 (CH 3 )][OTf] 和 [ cis- (η 5 -C 5 H 3 ) 2 (CMe 2 ) 2 }Ru 2 (κ 2 -(4,4'-二叔丁基)-2,2'-联吡啶) 2 (μ-CH 3 )][B(Ar F) ) 4]，已经合成和表征。当 CO 是辅助配体时，CH 3基团是末端并且易于迁移到 Cp 配体。在计算上，该甲基配合物具有两个带有配价键的 Ru(II) 中心，其中一个金属中心因甲基迁移到 Cp 配体的速率决定而减少。当辅助配体是二叔丁基联吡啶时，CH 3基团桥接两个钌中心，其中一个钌具有直接的Ru-C 键，另一个通过激动相互作用与CH 3基团相互作用。钌之间CH 3基团的交换具有低激活势垒。这里，添加酸，[H(OEt 2 ) 2][B(Ar F ) 4