Electron-Rich Cplr(biphenyl-2,2′-diyl) Complexes with π-Accepting Carbon Donor Ligands
Electron-Rich Cplr(biphenyl-2,2′-diyl) Complexes with π-Accepting Carbon Donor Ligands
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DOI：
10.1021/om300696t
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发表时间：
2012-10-22
期刊：
影响因子：
2.8
通讯作者：
Crabtree, Robert H.
中科院分区：
文献类型：
--
作者：
Graeupner, Jonathan;Brewster, Timothy P.;Crabtree, Robert H.
Cp*Ir-III 和 CpIrIII 配合物作为氧化转化催化剂引起了人们的兴趣，并且高氧化性铱物质被认为是催化水和 C-H 键氧化的关键中间体。强给电子配体组已被证明可以稳定 Ir-IV 配合物。我们描述了含有由一系列强供体碳基配体稳定的 CpIr(联苯-2,2'-二基) 部分的配合物的合成和反应性。这些配合物的氧化化学已通过电化学方法进行了表征，并且通过 X 波段 EPR 观察到了配合物 CpIr(biph)(p-CNCH2SO2C6H4CH3) 的单氧化 Ir-IV 物质。
Cp*Ir-III and CpIrIII complexes have attracted interest as catalysts for oxidative transformations, and highly oxidizing iridium species are postulated as key intermediates in both catalytic water and C-H bond oxidation. Strongly electron-donating ligand sets have been shown to stabilize Ir-IV complexes. We describe the synthesis and reactivity of complexes containing the CpIr(biphenyl-2,2'-diyl) moiety stabilized by a series of strong donor carbon-based ligands. The oxidation chemistry of these complexes has been characterized electrochemically, and a singly oxidized Ir-IV species has been observed by X-band EPR for the complex CpIr(biph)(p-CNCH2SO2C6H4CH3).