[Ir(CH=CHCH=CH(cyclic))(NCCH3)(CO)(PPh3)2]OTf | 849767-99-3

• 英文名称: [Ir(CH=CHCH=CH(cyclic))(NCCH3)(CO)(PPh3)2]OTf
• 英文别名: [Ir(CH=CHCH=CH)(NCCH3)(CO)(PPh3)2]OTf
• CAS: 849767-99-3
• 化学式: CF₃O₃S*C₄₃H₃₇IrNOP₂
• 分子量: 987.011
• InChiKey: OOPIHJJOOXDDJU-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 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：

  [Ir(CH=CHCH=CH(cyclic))(NCCH3)(CO)(PPh3)2]OTf 、 1,4-二乙炔基苯 在 N(CH₂CH₃)3 作用下， 以 氯仿 为溶剂， 以92%的产率得到
  参考文献：
  名称：

  Regio- and Stereoselective C−C Bond Formation between Alkynes:  Synthesis of Linear Dienynes from Alkynes

  摘要：

  Reactions of the iridacyclopentadienes [Ir(-CH=CHCH=CH)(NCCH3)(CO)(PPh3)(2)](+) (2a) and [Ir(-CH=C(CH2)(4)C=CH)(NCCH3)(CO)(PPh3)(2)](+) (2b) with RC=CH (R = C6H5, p-C6H4CH3) give linear conjugated dienynes (RCdropCCH=CHCH=CH2 (3) and RCdropCCH=C(CH2)(4)C=CH2 (5)) and benzene derivatives (RC6H5 (4) and RC6H3C6H8 (6, 6-aryl-1,2,3,4-tetrahydronaphthalene)). Linear conjugated dienynes 3 and 5 are exclusively obtained from the reactions of alkynyl iridacyclopentadienes [Ir(-CH=CHCH=CH)(CdropCR)(CO)(PPh3)(2)] (7) and [Ir(-CH=C(CH2)(4)C=CH)(CdropCR)(CO)(PPh3)(2)] (8) (R = C6H5 (a), p-C6H4CH3 (b), cyclohex 1-enyl (c)) with HOTf, respectively. The di- and trinuclear alkynyl iridacyclopentadienes p-C6H4(CdropCIr(-CH=CHCH=CH)L-3)(2) (9a), P-C6H4(CdropCIrCH=C(CH2)(4)C=CH)L-3)(2) (9b), and m,m-C6H3(CdropCIr(-CH=CHCH=CH)L-3)(3) (10) (L-3 = (CO)(PPh3)(2)) react with HOTf to produce the extended and conjugated dienynes p-C6H4(CdropCCH=CHCH=CH2)(2) (11), p-C6H4 (CdropCCH=C(CH2)(4)C=CH2)2 (12), and m,m-C6H3(CdropCCH=CHCH=CH2)(3) (13), respectively, in high yields. Iridacyclohexadienes [Ir(-CH=CHCH=CHC(=CH-p-C6H4R'))(CO)(PPh3)(2)]BF4 (17, R' = H (a), CH3 (b)) are obtained from the reactions of 7 with HBF4 through a C-C bond-forming reaction between the alpha-carbons of alkynyl and 1,3-butadiene-1,4-diyl ligands. Plausible reaction pathways are suggested for the C-C bond-forming reaction between RCdropCH and 1,3-butadiene-1,4-diyl ligands of iridacyclopentadienes to produce linear dienynes.

  DOI：

  10.1021/om020493b
• 作为产物：
  描述：

  、 三氟甲磺酸 、 乙腈 以 not given 为溶剂， 生成 [Ir(CH=CHCH=CH(cyclic))(NCCH3)(CO)(PPh3)2]OTf 、 苯乙炔
  参考文献：
  名称：

  Regio- and Stereoselective C−C Bond Formation between Alkynes:  Synthesis of Linear Dienynes from Alkynes

  摘要：

  Reactions of the iridacyclopentadienes [Ir(-CH=CHCH=CH)(NCCH3)(CO)(PPh3)(2)](+) (2a) and [Ir(-CH=C(CH2)(4)C=CH)(NCCH3)(CO)(PPh3)(2)](+) (2b) with RC=CH (R = C6H5, p-C6H4CH3) give linear conjugated dienynes (RCdropCCH=CHCH=CH2 (3) and RCdropCCH=C(CH2)(4)C=CH2 (5)) and benzene derivatives (RC6H5 (4) and RC6H3C6H8 (6, 6-aryl-1,2,3,4-tetrahydronaphthalene)). Linear conjugated dienynes 3 and 5 are exclusively obtained from the reactions of alkynyl iridacyclopentadienes [Ir(-CH=CHCH=CH)(CdropCR)(CO)(PPh3)(2)] (7) and [Ir(-CH=C(CH2)(4)C=CH)(CdropCR)(CO)(PPh3)(2)] (8) (R = C6H5 (a), p-C6H4CH3 (b), cyclohex 1-enyl (c)) with HOTf, respectively. The di- and trinuclear alkynyl iridacyclopentadienes p-C6H4(CdropCIr(-CH=CHCH=CH)L-3)(2) (9a), P-C6H4(CdropCIrCH=C(CH2)(4)C=CH)L-3)(2) (9b), and m,m-C6H3(CdropCIr(-CH=CHCH=CH)L-3)(3) (10) (L-3 = (CO)(PPh3)(2)) react with HOTf to produce the extended and conjugated dienynes p-C6H4(CdropCCH=CHCH=CH2)(2) (11), p-C6H4 (CdropCCH=C(CH2)(4)C=CH2)2 (12), and m,m-C6H3(CdropCCH=CHCH=CH2)(3) (13), respectively, in high yields. Iridacyclohexadienes [Ir(-CH=CHCH=CHC(=CH-p-C6H4R'))(CO)(PPh3)(2)]BF4 (17, R' = H (a), CH3 (b)) are obtained from the reactions of 7 with HBF4 through a C-C bond-forming reaction between the alpha-carbons of alkynyl and 1,3-butadiene-1,4-diyl ligands. Plausible reaction pathways are suggested for the C-C bond-forming reaction between RCdropCH and 1,3-butadiene-1,4-diyl ligands of iridacyclopentadienes to produce linear dienynes.

  DOI：

  10.1021/om020493b

文献信息

• Iridabenzenes from Iridacyclopentadienes:  Unusual C−C Bond Formation between Unsaturated Hydrocarbyl Ligands
  作者：Chong Shik Chin、Hyungeui Lee、Min-Sik Eum

  DOI：10.1021/om050529a

  日期：2005.9.1

  Iridabenzenes are produced by an unusual C−C coupling between the α-carbon of the alkynyl ligand and the δ-carbon of the neighboring 1,3-butadienyl ligand upon protonation of the β-carbon of the alkynyl ligand.

  炔基配体的β-碳质子化时，炔基配体的α-碳与相邻的1,3-丁二烯基配体的δ-碳之间存在异常的CC偶联作用，从而产生了铱苯。
• 1,1-Insertion of substituted alkynes into the Ir–O bond of η2-carboxylato iridium complexes
  作者：Chong Shik Chin、Hyungeui Lee、Myung Ki Lee、Soyoung Noh、Min-Sik Eum、Seunggweon Hong

  DOI：10.1016/j.jorganchem.2004.11.040

  日期：2005.3

  Alkyl-carbonyl-iridium [Ir(CH3)(CO)(eta(2) - O2CR ')(PPh3)(2)](+) (1, R ' = CH3, Ph, p-C6H4CH3) react with alkynes (RC &3bond; CH; R = Ph, p-C6H4CH3) in the presence of NEt3 to give acyl-alkynyl-iridium Ir(C(=O)CH3)(-C &3bond; CR)(eta(2) -O2CR ')(PPh3)(2) (4) which further react with RC &3bond; CH to give alkyl-carbonyl-cis-bis(alkynyl) iridium Ir(CH3)(CO)(C &3bond; CR)(2)(PPh3)(2) (5). cis-Bis(alkenyl)iridium complexes, Ir(-CH=CH2)(2)(eta(2) -O2CCH3)(PPh3)(2) (6) and Ir(-CH=CHCH=CH)(eta(2)-O2CCH3)PPh3)(2) (7) react with substituted alkynes RC &3bond; CH (R = Ph, p-C6H4CH3, cyclohex-1-enyl) to give cis-bis(alkynyl) Ir(C &3bond; CR)(2)(eta(2)-O2CCH2)(PPh3)(2) (9) that further react with RC &3bond; CH to undergo the alkyne insertion reaction into the Ir-O bond to produce iridacycles containing vinyl acetate ligands, Ir(C(=CHR)OC(CH3)=O)(-C &3bond; CR)(2)(PPh3)(2) (8). (c) 2004 Elsevier B.V. All rights reserved.