Modes of Activation of Organometallic Iridium Complexes for Catalytic   Water and C-H Oxidation

doi:10.1021/ic402390t

CORC > 北京大学 > 化学与分子工程学院

	Modes of Activation of Organometallic Iridium Complexes for Catalytic Water and C-H Oxidation
	Ingram, Andrew J. ; Wolk, Arron B. ; Flender, Cornelia ; Zhang, Jialing ; Johnson, Christopher J. ; Hintermair, Ulrich ; Crabtree, Robert H. ; Johnson, Mark A. ; Zare, Richard N.
刊名	inorganic chemistry
	2014
关键词	DESORPTION ELECTROSPRAY-IONIZATION MASS-SPECTROMETRY GAS-PHASE INFRARED PHOTODISSOCIATION PROTEIN COMPLEXES SODIUM PERIODATE ION SAMPLING/IONIZATION SPECTROSCOPY PRECATALYSTS
DOI	10.1021/ic402390t
英文摘要	Sodium periodate (NaIO4) is added to CpIr-III (Cp = C5Me5-) or (cod)Ir-I (cod = cyclooctadiene) complexes, which are water and C-H oxidation catalyst precursors, and the resulting aqueous reaction is investigated from milliseconds to seconds using desorption electrospray ionization, electrosonic spray ionization, and cryogenic ion vibrational predissociation spectroscopy. Extensive oxidation of the Cp* ligand is observed, likely beginning with electrophilic C-H hydroxylation of a Cp* methyl group followed by nonselective pathways of further oxidative degradation. Evidence is presented that the supporting chelate ligand in CpIr(chelate) precursors influences the course of oxidation and is neither eliminated from the coordination sphere nor oxidatively transformed. Isomeric products of initial Cp oxidation are identified and structurally characterized by vibrational spectroscopy in conjunction with density functional theory (DFT) modeling. Less extensive but more rapid oxidation of the cod ligand is also observed in the (cod)Ir-I complexes. The observations are consistent with the proposed role of Cp* and cod as sacrificial placeholder ligands that are oxidatively removed from the precursor complexes under catalytic conditions.; Chemistry, Inorganic & Nuclear; SCI(E); 9; ARTICLE; mark.johnson@yale.edu; zare@stanford.edu; 1; 423-433; 53
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/216840]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Ingram, Andrew J.,Wolk, Arron B.,Flender, Cornelia,et al. Modes of Activation of Organometallic Iridium Complexes for Catalytic Water and C-H Oxidation[J]. inorganic chemistry,2014.
APA	Ingram, Andrew J..,Wolk, Arron B..,Flender, Cornelia.,Zhang, Jialing.,Johnson, Christopher J..,...&Zare, Richard N..(2014).Modes of Activation of Organometallic Iridium Complexes for Catalytic Water and C-H Oxidation.inorganic chemistry.
MLA	Ingram, Andrew J.,et al."Modes of Activation of Organometallic Iridium Complexes for Catalytic Water and C-H Oxidation".inorganic chemistry (2014).