On the Trail of CrO2Cl2 in Its Reactions with Organic Compounds

Limberg, Christian

doi:10.1002/1521-3765(20000616)6:12<2083::aid-chem2083>3.0.co;2-i

Cited by 28 publications

(16 citation statements)

References 11 publications

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“…Chemical reactions of the oxo ligands of the uranyl dication [UO 2 ] 2+ are rare due to the strongly covalent and linear O=U=O bonding and, as a consequence, over fifty percent of known uranium compounds incorporate this highly stable motif 1 . In contrast, the oxo groups of the transition metal congeners [MO 2 ] 2+ (M = Cr, Mo, W) can be highly reactive, and undergo a myriad of oxidation and oxygenation reactions with substrates as inert as hydrocarbons 2,3 . Nevertheless, reduction and oxofunctionalisation reactions of the uranyl are becoming increasingly important, particularly as there is a need to understand the chemical reactions and mechanisms that occur during the immobilisation of uranium in the environment and as a result of photoactivation of the ion, upon which it becomes a potent oxidant 4,5 .…”

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confidence: 99%

Uranyl oxo activation and functionalization by metal cation coordination

et al. 2010

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The oxo groups in the uranyl ion [UO(2)](2+)-one of many oxo cations formed by metals from across the periodic table-are particularly inert, which explains the dominance of this ion in the laboratory and its persistence as an environmental contaminant. In contrast, transition metal oxo (M=O) compounds can be highly reactive and carry out difficult reactions such as the oxygenation of hydrocarbons. Here we show how the sequential addition of a lithium metal base to the uranyl ion constrained in a 'Pacman' environment results in lithium coordination to the U=O bonds and single-electron reduction. This reaction depends on the nature and stoichiometry of the lithium reagent and suggests that competing reduction and C-H bond activation reactions are occurring.

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Section: Main Textmentioning

confidence: 99%

Uranyl oxo activation and functionalization by metal cation coordination

et al. 2010

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“…[1][2][3][4][5] In a series of studies Ault and co-workers explored the reactions of CrO 2 Cl 2 with a variety of organic molecules and donor ligands at very low temperatures using matrix isolation IR spectroscopic techniques. [6][7][8][9][10][11] More conventional coordination studies are limited and the reports contradictory.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Properties, and Structures of Chromium(VI) and Chromium(V) Complexes with Heterocyclic Nitrogen Ligands

Levason

Reid

Zhang

2013

Zeitschrift anorg allge chemie

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Abstract. The reaction of CrO 2 Cl 2 with 2,2Ј-bipyridyl or 1,10-phenanthroline (diimine) in CCl 4 or anhydrous CH 3 CO 2 H solution, produces orange-brown diamagnetic [CrO 2 Cl 2 (diimine)]. The X-ray structure of [CrO 2 Cl 2 (2,2Ј-bipy)] shows a six-coordinate central chromium(VI) atom with cis-dioxo groups trans to the diimine. In contrast, the diimines react with CrO 3 in CH 3 CO 2 H / conc. aqueous HCl to form bright red paramagnetic Cr V complexes, [CrOCl 3 (diimine)]. The X-ray structure of [CrOCl 3 (2,2Ј-bipy)] shows a six-coordinate central chromium atom with mer-chlorines and the diimine trans to O/Cl. The

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“…CrO 2 Cl 2 is a very strong oxidizing agent, a process that has been utilized extensively for organic synthesis. [4][5][6] Of particular interest is the selectivity of the oxidation of organic compounds and the specificity of the product formed. CrO 2 Cl 2 and similar metal oxo compounds are able to transfer their oxygen atom to certain olefins and hydrocarbons.…”

Section: Introductionmentioning

confidence: 99%

Infrared matrix isolation study of the oxidation of H₂S by CrCl₂O₂

Thompson

Goldberg

Ault

2006

Phys. Chem. Chem. Phys.

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The thermal and photochemical reactions between CrO2Cl2 and H2S have been investigated using matrix isolation infrared spectroscopy. Twin-jet co-deposition of the two reagents into argon matrices at 14 K followed by irradiation with light of lambda > 300 nm led to the growth of a number of new bands. These have been assigned to the HSOH-CrCl2O complex, and to SO2. These assignments were supported by deuterium isotopic substitution and high level density functional calculations. Merged-jet deposition with the reaction zone at temperatures above 125 degrees C led to substantial yields of SO2 and HCl, as well as the complex of HCl with excess parent H2S. The evidence suggests that the thermal and photochemical reactions may follow different pathways.

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On the Trail of CrO2Cl2 in Its Reactions with Organic Compounds

Cited by 28 publications

References 11 publications

Uranyl oxo activation and functionalization by metal cation coordination

Uranyl oxo activation and functionalization by metal cation coordination

Synthesis, Properties, and Structures of Chromium(VI) and Chromium(V) Complexes with Heterocyclic Nitrogen Ligands

Infrared matrix isolation study of the oxidation of H₂S by CrCl₂O₂

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On the Trail of CrO2Cl2 in Its Reactions with Organic Compounds

Cited by 28 publications

References 11 publications

Uranyl oxo activation and functionalization by metal cation coordination

Uranyl oxo activation and functionalization by metal cation coordination

Synthesis, Properties, and Structures of Chromium(VI) and Chromium(V) Complexes with Heterocyclic Nitrogen Ligands

Infrared matrix isolation study of the oxidation of H2S by CrCl2O2

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Infrared matrix isolation study of the oxidation of H₂S by CrCl₂O₂