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We are sorry, we are unable to retrieve the citation details for this record.A fragile zwitterionic phosphasilene as a transfer agent of the elusive parent phosphinidene (:PH).
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2013 Aug 14;135(32):11795-8. doi: 10.1021/ja4072699. Epub
2013 Aug 1.A fragile zwitterionic phosphasilene as a transfer agent of the elusive parent phosphinidene (:PH).1, , , , , .1Metalorganics and Inorganic Materials, Department of Chemistry, Technische Universit?t Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623 Berlin, Germany.AbstractThe simplest parent phosphinidene, :PH (1), has been observed only in the gas phase or low temperature matrices and has escaped rigorous characterization because of its high reactivity. Its liberation and transfer to an unsaturated organic molecule in solution has now been accomplished by taking advantage of the facile homolytic bond cleavage of the fragile Si═P bond of the first zwitterionic phosphasilene LSi=PH (8) (L = CH[(C═CH2)CMe(NAr)2]; Ar = 2,6-(i)Pr2C6H3). The latter bears two highly localized lone pairs on the phosphorus atom due to the LSi═PH
LSi(+)-PH(-) resonance structures. Strikingly, the dissociation of 8 in hydrocarbon solutions occurs even at room temperature, affording the N-heterocyclic silylene LSi: (9) and 1, which leads to oligomeric [PH]n clusters in the absence of a trapping agent. However, in the presence of an N-heterocyclic carbene as an unsaturated organic substrate, the fragile phosphasilene 8 acts as a :PH transfer reagent, resulting in the formation of silylene 9 and phosphaalkene 11 bearing a terminal PH moiety. PMID:
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Infrared absorption of cis‐ and trans‐alkali‐metal peroxynitrites (MOONO, M=Li, Na, and K) in solid argon
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J. Chem. Phys. 103, 4026 (Fri Sep 08 00:00:00 UTC 1995);
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Potassium nitrate (KNO3) isolated in solid argon at 13 K was irradiated with emission from an ArF excimer laser at 193 nm. Recombination of the photofragments led to formation of both cis‐ and trans‐potassium peroxynitrites (KOONO). The cyclic conformer, cis‐KOONO, absorbs at 2.3, 831.6, and 749.1 cm-1, whereas trans‐KOONO absorbs at 7.4, and 602.2 cm-1. The assignments are based on observed 18O‐ and 15N‐isotopic shifts and comparison with similar compounds, cis–cis and trans–perp HOONO. Ab initio calculations using density functional theory at a Becke3LYP level predicted similar line positions and isotopic shifts for both conformers. Photoconversion among these three isomers was achieved at various wavelengths and pe cis‐KOONO was photolyzed readily at 308 nm, whereas trans‐KOONO increased slightly in intensity initially and was eventually transformed to KNO3 on prolonged irradiation. Similar results were obtained for LiNO3 and NaNO3; cis‐LiOONO and cis‐NaOONO absorb at (22.0), 966.2, 874.2, 792.3 cm-1 and (34.6), 961.4, 840.7, (770.9, 768.7) cm-1, respectively, whereas trans‐LiOONO and trans‐NaOONO absorb at (80.4), (998.3, 995.6), 600.4 cm-1 and (40.6), (996.3, 994.1), (609.4, 607.4) cm-1, the numbers in parentheses are due to line splitting.
Received Mon Apr 17 00:00:00 UTC 1995
Accepted Fri Jun 02 00:00:00 UTC 1995
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Infrared absorption of cis‐ and trans‐alkali‐metal peroxynitrites (MOONO, M=Li, Na, and K) in solid argon
J. Chem. Phys. 103, 4026 (Fri Sep 08 00:00:00 UTC 1995);
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Scitation: Infrared absorption of cis‐ and trans‐alkali‐metal peroxynitrites (MOONO, M=Li, Na, and K) in solid argon
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