[Ir(PMe3)3Cl(η(2)-cyclooctene)] | 59390-28-2

• 英文名称: [Ir(PMe3)3Cl(η(2)-cyclooctene)]
• 英文别名: Ir(cyclooctene)(PMe3)Cl；(η-cyclooctene)IrCl(PMe3)3；[Ir(Cl)(PMe3)3(η2-cyclooctene)]；(η2-cyclooctene)(Cl)Ir(PMe3)3
• CAS: 59390-28-2
• 化学式: C₁₇H₄₁ClIrP₃
• 分子量: 566.107
• InChiKey: HOXXPGINKSJRKV-XBOSCTMBSA-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

• 作为反应物：
  描述：

  [Ir(PMe3)3Cl(η(2)-cyclooctene)] 以 甲苯 为溶剂， 生成 (Cl)Ir(PMe3)3
  参考文献：
  名称：

  Oxidative Addition of Water and Aliphatic Alcohols by IrCl(trialkylphosphine)₃

  摘要：

  Oxidative addition of aliphatic alcohols to (C8H14)IrCl(PMe3)(3) in benzene yields the cis-hydridoalkoxo products mer-cis-HIr(OR)Cl(PMe3)(3) (R = Me, Et, 1-pentyl, 2-propyl) The analogous hydroxo complex is prepared by oxidative addition of water in THF. The addition rate depends on the nature of the alcohol (methanol > 1-pentanol >> 2-propanol and methanol > water). The reaction is retarded in polar media but accelerated by protic cosolvents. Anionic ligand redistribution involving chloride and alkoxide (or hydroxide) competes with the oxidative addition reaction. A detailed kinetic study suggests that the 16-electron 10(PMe3)(3) is the species undergoing the oxidative addition, and mer-cis-HIr(OR)Cl(PMe3)(3) is the kinetic product. The reaction proceeds by a single-step nucleophilic attack of the metal on the O-H proton pi-Donation by chloride stabilizes the transition state and governs the stereochemical course of the reaction Protic solvent aggregation in the transition state in an apolar medium is suggested mer-cis-HIr(OH)Cl(PEt3)(3), obtained by water addition to IrCl(PEt3)(3), was crystallographically characterized, showing an unusual hydrophobic cage around the hydride ligand.

  DOI：

  10.1021/ja012611c
• 作为产物：
  描述：

  三甲基膦 、 chlorobis(cyclooctene)-iridium(I) dimer 以 甲苯 为溶剂， 以53%的产率得到[Ir(PMe3)3Cl(η(2)-cyclooctene)]
  参考文献：
  名称：

  Oxidative Addition of Water and Aliphatic Alcohols by IrCl(trialkylphosphine)₃

  摘要：

  Oxidative addition of aliphatic alcohols to (C8H14)IrCl(PMe3)(3) in benzene yields the cis-hydridoalkoxo products mer-cis-HIr(OR)Cl(PMe3)(3) (R = Me, Et, 1-pentyl, 2-propyl) The analogous hydroxo complex is prepared by oxidative addition of water in THF. The addition rate depends on the nature of the alcohol (methanol > 1-pentanol >> 2-propanol and methanol > water). The reaction is retarded in polar media but accelerated by protic cosolvents. Anionic ligand redistribution involving chloride and alkoxide (or hydroxide) competes with the oxidative addition reaction. A detailed kinetic study suggests that the 16-electron 10(PMe3)(3) is the species undergoing the oxidative addition, and mer-cis-HIr(OR)Cl(PMe3)(3) is the kinetic product. The reaction proceeds by a single-step nucleophilic attack of the metal on the O-H proton pi-Donation by chloride stabilizes the transition state and governs the stereochemical course of the reaction Protic solvent aggregation in the transition state in an apolar medium is suggested mer-cis-HIr(OH)Cl(PEt3)(3), obtained by water addition to IrCl(PEt3)(3), was crystallographically characterized, showing an unusual hydrophobic cage around the hydride ligand.

  DOI：

  10.1021/ja012611c

文献信息

• Synthesis and x-ray structure of a simple metallaoxetane. Metal-based selectivity in oxidative addition
  作者：Andrei A. Zlota、Felix Frolow、David Milstein

  DOI：10.1021/ja00173a047

  日期：1990.8

  La reaction d'3-halogeno-2-methyl propan-2-ol avec le complexe RhL 3 Cl (L=PPh 3 ) donne le complexe (PPh 3 ) 3 (Br)(Cl) (2-hydroxy-2-methylpropyl) du rhodium qui reagit ensuite avec (Me 3 Si) 2 NK pour donner le complexe (PPh 3 ) 3 (Br) (3,3-dimethyl) 1-Oxa-2-rhodacyclobutane. Etude par diffraction de ces deux complexes

  La 反应 d'3-halogeno-2-methyl propan-2-ol avec le complexe RhL 3 Cl (L=PPh 3 ) donne le complexe (PPh 3 ) 3 (Br)(Cl) (2-羟基-2-甲基丙基) ) du rhodium qui reagit ensuite avec (Me 3 Si) 2 NK Pour donner le complexe (PPh 3 ) 3 (Br) (3,3-二甲基) 1-Oxa-2-rhodacyclobutane。练习曲 par 衍射 de ces deux complexes
• Synthesis and Characterization of Fused-Ring Iridapyrroles
  作者：John R. Bleeke、Phawit Putprasert、Todsapon Thananatthanachon、Nigam P. Rath

  DOI：10.1021/om8008712

  日期：2008.11.24

  Treatment of aromatic nitriles with methyllithium produces N-lithiated imine reagents which, when reacted with (eta(2)-cyclooctene)(Cl)Ir(PMe(3))(3), generate fused iridaazacycles via ortho-metallation. Mono-protonation of these iridaazacycles produces fused iridapyrrole derivatives, while di-protonation leads to several different pathways.

  用甲基锂处理芳香腈会产生 N 锂化亚胺试剂，当与 (eta(2)-环辛烯)(Cl)Ir(PMe(3))(3) 反应时，通过邻位金属化生成稠合的 iridaazacycles。这些 iridaazacycles 的单质子化产生稠合的 iridapyrrole 衍生物，而二质子化导致几种不同的途径。
• Oxidative addition of a B—B bond by an iridium(I) complex: molecular structure of <i>mer</i>-<i>cis</i>-[Ir(PMe₃)₃Cl(Bcat)₂]
  作者：Chaoyang Dai、Graham Stringer、Todd B. Marder、R. Thomas Baker、Andrew J. Scott、William Clegg、Nicholas C. Norman

  DOI：10.1139/v96-231

  日期：1996.11.1

  The B—B bond in B2Cat2 (cat = 1,2-O2C6H4) is readily activated by [Ir(PMe3)3Cl(COE)] (COE = η2-cyclooctene) (1) to yield a novel iridium(III) bis(boryl) complex mer-cis-[Ir(PMe3)3Cl(Bcat)2] (2). This complex is the first structurally characterized iridium bis(boryl) compound, and is the first metal bis(boryl) complex for which two distinct boryl group environments are observed in solution. Colourless

  B2Cat2 (cat = 1,2-O2C6H4) 中的 B-B 键很容易被 [Ir(PMe3)3Cl(COE)] (COE = η2-环辛烯) (1) 激活，产生一种新的铱 (III) bis( Boryl) 络合物 mer-cis-[Ir(PMe3)3Cl(Bcat)2] (2)。该配合物是第一个结构特征化的铱双（硼基）化合物，并且是第一个在溶液中观察到两种不同硼基环境的金属双（硼基）配合物。2 的无色晶体为单斜晶系，P21/n，晶胞尺寸 a = 8.9638(7) A，b = 32.197(2) A，c = 9.3980(7) A，β = 90.385(2)°。关键词：铱、硼、二硼、硼基、氧化加成、X射线结构、三甲基膦。
• Synthesis of rhodium and iridium boryl complexes via oxidative addition of haloboranes
  作者：Fábio E.S. Souza、Paul Nguyen、Todd B. Marder、Andrew J. Scott、William Clegg

  DOI：10.1016/j.ica.2004.09.007

  日期：2005.3

  B-Chlorocatecholborane undergoes oxidative addition to M(PR3)3Cl (M = Rh, R = Me; M = Ir, R = Me, Et) yielding six-coordinate complexes of general formula mer,cis-(PR3)3Cl2M(BO2C6H4). The same M(PR3)3Cl complexes also react with B-bromocatecholborane to give a mixture of metal boryl homo- and heterodihalides (PR3)3X1X2M(BO2C6H4) (X1, X2 = Cl, Br), and the observed disproportionation is believed to

  B-氯邻苯二甲硼烷经过氧化加成至M（PR 3）3 Cl（M = Rh，R = Me; M = Ir，R = Me，Et）生成通式为mer的六配位配合物，顺式-（PR 3）3 Cl 2 M（BO 2 C 6 H 4）。相同的M（PR 3）3 Cl络合物也与B-溴儿茶酚硼烷反应生成金属硼基均二卤化物和杂二卤化物（PR 3）3 X 1 X 2 M（BO 2 C 6 H 4）（X 1，X 2  ＝ Cl，Br），并且观察到的歧化被认为涉及异核卤化物桥接的中间体的形成。烯烃4-乙烯基茴香醚在环境温度下无法与六配位18电子（PR 3）3 Cl 2 M（BO 2 C 6 H 4）配合物反应。
• Synthesis, Structure, and Spectroscopy of Silaallyl− and Silapentadienyl−Iridium−Phosphine Complexes¹
  作者：John R. Bleeke、Todsapon Thananatthanachon、Nigam P. Rath

  DOI：10.1021/om700487n

  日期：2007.7.30

  Silaallyl− and silapentadienyl−iridium−phosphine complexes have been synthesized via the reaction of “(Me)Ir(PMe3)3” with vinyl- and butadienyldimethylsilanes. Upon heating, these complexes lose methane and undergo a variety of reactions, including C−H bond activation to produce a five-membered iridasilacycle, CC bond coordination to generate an η1,η2-silapentadienyl ligand, and decomposition.

  通过“（Me）Ir（PMe 3）3 ”与乙烯基和丁二烯基二甲基硅烷的反应合成了硅氮丙烯基和硅戊二烯基铱膦复合物。在加热时，这些配合物失去甲烷和经历各种反应，包括C-H键活化，以产生一个五元iridasilacycle，C C键协调以产生η 1，η 2 -silapentadienyl配体，和分解。