具有吸电子碳供体配体的富电子CpIr（联苯-2,2'-二基）配合物
Electron-Rich CpIr(biphenyl-2,2'-diyl) Complexes with -Accepting Carbon Donor Ligands.
作者信息
Graeupner Jonathan, Brewster Timothy P, Blakemore James D, Schley Nathan D, Thomsen Julianne M, Brudvig Gary W, Hazari Nilay, Crabtree Robert H
机构信息
Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, United States.
出版信息
Organometallics. 2012 Oct 20;31(20):7158-7164. doi: 10.1021/om300696t.
Cp*Ir and CpIr 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 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 species has been observed by X-band EPR for the complex CpIr(biph)(CNCHSOCHCH).
茂环戊二烯基铱（Cp*Ir）和茂环戊二烯基铱（CpIr）配合物作为氧化转化催化剂已引起关注，高氧化性铱物种被假定为催化水氧化和碳氢键氧化的关键中间体。已表明强给电子配体基团可稳定铱配合物。我们描述了含有由一系列强给电子碳基配体稳定的CpIr（联苯-2,2'-二基）部分的配合物的合成及反应活性。这些配合物的氧化化学性质已通过电化学进行了表征，并且通过X波段电子顺磁共振（EPR）观察到配合物CpIr（联苯）（氰基甲基磺酰基氧代环己烯）存在单氧化态铱物种。
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