Unusual Reactivity of the Radical Cations of Some Simple Trivalent Organophosphorus Compounds toward Dimethyl Disulfide and Dimethyl Diselenide

1996 ◽  
Vol 118 (6) ◽  
pp. 1408-1412 ◽  
Author(s):  
Rebecca L. Smith ◽  
Andreas Schweighofer ◽  
Helmut Keck ◽  
Wilhelm Kuchen ◽  
Hilkka I. Kenttämaa
Keyword(s):  
Organophosphorus Compounds ◽  
Dimethyl Disulfide ◽  
Radical Cations ◽  
Dimethyl Diselenide

scholarly journals Distinguishing conventional and distonic radical cations by using dimethyl diselenide

1996 ◽  
Vol 7 (12) ◽  
pp. 1245-1250 ◽  
Author(s):  
Kami K. Thoen ◽  
Brandon J. Beasley ◽  
Rebecca L. Smith ◽  
Hilkka I. Kenttämaa
Keyword(s):  
Radical Cations ◽  
Dimethyl Diselenide

scholarly journals Probing Coherent Vibrations of Organic Phosphonate Radical Cations with Femtosecond Time-Resolved Mass Spectrometry

Molecules ◽  
2019 ◽  
Vol 24 (3) ◽  
pp. 509 ◽  
Author(s):  
Derrick Ampadu Boateng ◽  
Mi’Kayla Word ◽  
Katharine Tibbetts
Keyword(s):  
Mass Spectrometry ◽  
Organophosphorus Compounds ◽  
Vibrational Excitation ◽  
Radical Cations ◽  
Time Resolved ◽  
Oscillatory Dynamics ◽  
Phosphate Backbone ◽  
Molecular Radical ◽  
Ion Yields ◽  
Organic Phosphonate

Organic phosphates and phosphonates are present in a number of cellular components that can be damaged by exposure to ionizing radiation. This work reports femtosecond time-resolved mass spectrometry (FTRMS) studies of three organic phosphonate radical cations that model the DNA sugar-phosphate backbone: dimethyl methylphosphonate (DMMP), diethyl methylphosphonate (DEMP), and diisopropyl methylphosphonate (DIMP). Upon ionization, each molecular radical cation exhibits unique oscillatory dynamics in its ion yields resulting from coherent vibrational excitation. DMMP has particularly well-resolved 45 fs ( 732 ± 28 cm − 1 ) oscillations with a weak feature at 610–650 cm − 1 , while DIMP exhibits bimodal oscillations with a period of ∼55 fs and two frequency features at 554 ± 28 and 670–720 cm − 1 . In contrast, the oscillations in DEMP decay too rapidly for effective resolution. The low- and high-frequency oscillations in DMMP and DIMP are assigned to coherent excitation of the symmetric O–P–O bend and P–C stretch, respectively. The observation of the same ionization-induced coherently excited vibrations in related molecules suggests a possible common excitation pathway in ionized organophosphorus compounds of biological relevance, while the distinct oscillatory dynamics in each molecule points to the potential use of FTRMS to distinguish among fragment ions produced by related molecules.

ChemInform Abstract: The Identification of Distonic Radical Cations on the Basis of a Reaction with Dimethyl Disulfide

ChemInform ◽  
2010 ◽  
Vol 24 (7) ◽  
pp. no-no
Author(s):  
K. M. STIRK ◽  
J. C. ORLOWSKI ◽  
D. T. LEECK ◽  
H. I. KENTTAEMAA
Keyword(s):  
Dimethyl Disulfide ◽  
Radical Cations

The identification of distonic radical cations on the basis of a reaction with dimethyl disulfide

1992 ◽  
Vol 114 (22) ◽  
pp. 8604-8606 ◽  
Author(s):  
Krista M. Stirk ◽  
Joseph C. Orlowski ◽  
Diane T. Leeck ◽  
H. I. Kenttamaa
Keyword(s):  
Dimethyl Disulfide ◽  
Radical Cations

scholarly journals Electrochemical C–H phosphorylation of arenes in continuous flow suitable for late-stage functionalization

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Hao Long ◽  
Chong Huang ◽  
Yun-Tao Zheng ◽  
Zhao-Yu Li ◽  
Liang-Hua Jie ◽  
...  
Keyword(s):  
Late Stage ◽  
Continuous Flow ◽  
Organophosphorus Compounds ◽  
Continuous Production ◽  
Radical Cations ◽  
High Reactivity ◽  
Transition Metal Catalysts ◽  
Phosphorus Compounds ◽  
Chemical Oxidants ◽  
Phosphorylation Reaction

AbstractThe development of efficient and sustainable methods for carbon-phosphorus bond formation is of great importance due to the wide application of organophosphorus compounds in chemistry, material sciences and biology. Previous C–H phosphorylation reactions under nonelectrochemical or electrochemical conditions require directing groups, transition metal catalysts, or chemical oxidants and suffer from limited scope. Herein we disclose a catalyst- and external oxidant-free, electrochemical C–H phosphorylation reaction of arenes in continuous flow for the synthesis of aryl phosphorus compounds. The C–P bond is formed through the reaction of arenes with anodically generated P-radical cations, a class of reactive intermediates remained unexplored for synthesis despite intensive studies of P-radicals. The high reactivity of the P-radical cations coupled with the mild conditions of the electrosynthesis ensures not only efficient reactions of arenes of diverse electronic properties but also selective late-stage functionalization of complex natural products and bioactive compounds. The synthetic utility of the electrochemical method is further demonstrated by the continuous production of 55.0 grams of one of the phosphonate products.

Reactivity Trends in the Gas Phase Addition of Acetylene to N-protonated Aryl Radical Cations

2020 ◽  
Author(s):  
Oisin Shiels ◽  
P. D. Kelly ◽  
Cameron C. Bright ◽  
Berwyck L. J. Poad ◽  
Stephen Blanksby ◽  
...  
Keyword(s):  
Gas Phase ◽  
Ion Trap ◽  
Radical Cations ◽  
Rate Coefficients ◽  
Similar Process ◽  
Ion Molecule Reactions ◽  
Aromatic Radicals ◽  
Polycyclic Aromatic ◽  
Gas Phase Ion ◽  
Type Radical

<div> <div> <div> <p>A key step in gas-phase polycyclic aromatic hydrocarbon (PAH) formation involves the addition of acetylene (or other alkyne) to σ-type aromatic radicals, with successive additions yielding more complex PAHs. A similar process can happen for N- containing aromatics. In cold diffuse environments, such as the interstellar medium, rates of radical addition may be enhanced when the σ-type radical is charged. This paper investigates the gas-phase ion-molecule reactions of acetylene with nine aromatic distonic σ-type radical cations derived from pyridinium (Pyr), anilinium (Anl) and benzonitrilium (Bzn) ions. Three isomers are studied in each case (radical sites at the ortho, meta and para positions). Using a room temperature ion trap, second-order rate coefficients, product branching ratios and reaction efficiencies are reported. </p> </div> </div> </div>

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