[(2,6-(t-Bu2PO)2C5H3N)Ir(H)2][tetrakis(3,5-bis(trifluoromethyl)phenyl)borate] | 1361399-42-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [(2,6-(t-Bu2PO)2C5H3N)Ir(H)2][tetrakis(3,5-bis(trifluoromethyl)phenyl)borate]
• CAS: 1361399-42-9
• 化学式: C₂₁H₄₁IrNO₂P₂*C₃₂H₁₂BF₂₄
• 分子量: 1456.95
• InChiKey: AYOLRXNMYBYMGU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  以 二氯甲烷-D2 为溶剂， 生成 [(2,6-(t-Bu2PO)2C5H3N)Ir(H)2][tetrakis(3,5-bis(trifluoromethyl)phenyl)borate]
  参考文献：
  名称：

  Mechanism of Hydrogenolysis of an Iridium–Methyl Bond: Evidence for a Methane Complex Intermediate

  摘要：

  Evidence for key a-complex intermediates in the hydrogenolysis of the iridium methyl bond of (PONOP)Ir(H)(Me)(+) (1) [PONOP = 2,6-bis(di-tert-butylphosphinito)pyridine] has been obtained. The initially formed eta(2)-H-2 complex, 2, was directly observed upon treatment of 1 with H-2, and evidence for reversible formation of a a-methane complex, 5, was obtained through deuterium scrambling from eta(2)-D-2 in 2-d(2) into the methyl group of 2 prior to methane loss. This sequence of reactions was modeled by density functional theory calculations. The transition state for formation of 5 from 2 showed significant shortening of the Ir-H bond for the hydrogen being transferred; no true Ir(V) trihydride intermediate could be located. Barriers to methane loss from 2 were compared to those of 1 and the six-coordinate species (PONOP)Ir(H)(Me)(CO)(+) and (PONOP)Ir(H)(Me)(Cl).

  DOI：

  10.1021/ja310982v

文献信息

• Dihydrogen Complexes of Iridium and Rhodium
  作者：Michael Findlater、Katherine M. Schultz、Wesley H. Bernskoetter、Alison Cartwright-Sykes、D. Michael Heinekey、Maurice Brookhart

  DOI：10.1021/ic202630x

  日期：2012.4.16

  interaction was probed using NMR spectroscopic studies. Complexes 1-H3, 2-H2, and 4-H2 retain the H–H bond and are classified as η2-dihydrogen adducts. In contrast, complex 3-H2 is best described as a classical dihydride system. The presence of bound dihydrogen was determined using both T1 and 1JHD coupling values: T1 = 14 ms, 1JHD = 33 Hz for the dihydrogen ligand in 1-H3, T1(min) = 23 ms, 1JHD = 32 Hz for

  合成了一系列铱和铑钳位配合物，并对其进行了表征：[（POCOP）Ir（H）（H 2）] [BARhref=https://www.molaid.com/MS_77868 target="_blank">BAr f 4 ]（1-H 3），（POCOP）Rh（H 2）（2- H 2），[（PONOP）Ir（C 2 H 4）] [BARhref=https://www.molaid.com/MS_77868 target="_blank">BAr f 4 ]（3-C 2 H 4），[（PONOP）Ir（H）2）] [BARhref=https://www.molaid.com/MS_77868 target="_blank">BAr f 4 ]（3-H 2），[（PONOP）Rh（C 2 H 4）] [BARhref=https://www.molaid.com/MS_77868 target="_blank">BAr f 4 ]（4-C 2 H 4）和[（PONOP）的Rh（H 2）] [BAR ˚F 4 ]（4-H 2）（POCOP =κ 3 -C 6 ħ 3 -2,6- [OP（吨丁基）2 ] 2 ; PONOP = 2,6-（t Bu 2 PO）2 C 5 H 3 N； BARhref=https://www.molaid.com/MS_77868 target="_blank">BAr f 4 =四（3,5-三氟甲基苯基）硼酸酯。使用NMR光谱学研究了二氢与金属相互作用的性质。络合物1-H 3， 2-H 2，和4-H 2保留H-H键和被分类为η