Matches in SemOpenAlex for { <https://semopenalex.org/work/W2062382364> ?p ?o ?g. }
- W2062382364 endingPage "8278" @default.
- W2062382364 startingPage "8271" @default.
- W2062382364 abstract "A series of para-substituted N-methyl-N-phenylnitrenium ions (N-(4-biphenylyl)-N-methylnitrenium ion, N-(4-chlorophenyl)-N-methylnitrenium ion, N-(4-methoxyphenyl)-N-methylnitrenium ion, and N-(4-methylphenyl)-N-methylnitrenium ion) were generated through photolysis of the appropriately substituted 1-aminopyridinium salt. Laser flash photolysis using UV−vis detection as well as photoproduct analysis verified that the expected nitrenium ions were formed cleanly and rapidly following photolysis. Laser flash photolysis with time-resolved infrared detection allowed for structural characterization of the nitrenium ions through observation of a symmetrical aromatic CC stretch in the region 1580−1628 cm-1. The specific frequencies reflect the degree of quinoidal character present in each phenylnitrenium ion (i.e., the degree to which the nitrenium ion resembles a 4-iminocyclohexa-2,5-dienyl cation). The 4-methoxy derivative shows the highest frequency CC stretch, indicating that this strongly π-electron-donating substituent imparts more quinoidal character, and the 4-chloro derivative shows the lowest frequency CC stretch, suggesting that it possesses the least quinoidal character. Quantum calculations using density functional theory (BPW91/cc-pVDZ) were carried out on the same nitrenium ions. The theoretically derived IR frequencies showed excellent quantitative agreement with the experiment. The computed structures show significant bond length alternation in the phenyl rings, shortened C−N bond lengths, and substantial positive charge delocalization into the phenyl rings. All of these effects are more pronounced with increasing π-donating character of the ring substituent. Arylnitrenium ions are well described as 4-iminocyclohexa-2,5-dienyl cations." @default.
- W2062382364 created "2016-06-24" @default.
- W2062382364 creator A5003289867 @default.
- W2062382364 creator A5021271650 @default.
- W2062382364 creator A5047937683 @default.
- W2062382364 creator A5048985028 @default.
- W2062382364 creator A5061078135 @default.
- W2062382364 creator A5063906638 @default.
- W2062382364 creator A5072216093 @default.
- W2062382364 creator A5091872913 @default.
- W2062382364 date "2000-08-01" @default.
- W2062382364 modified "2023-10-16" @default.
- W2062382364 title "Structures of Reactive Nitrenium Ions: Time-Resolved Infrared Laser Flash Photolysis and Computational Studies of Substituted <i>N</i>-Methyl-<i>N</i>-arylnitrenium Ions" @default.
- W2062382364 cites W1965182882 @default.
- W2062382364 cites W1975081044 @default.
- W2062382364 cites W1976945425 @default.
- W2062382364 cites W1979371251 @default.
- W2062382364 cites W1989675597 @default.
- W2062382364 cites W1990719402 @default.
- W2062382364 cites W1992658247 @default.
- W2062382364 cites W1994164662 @default.
- W2062382364 cites W2001206467 @default.
- W2062382364 cites W2001970643 @default.
- W2062382364 cites W2026034085 @default.
- W2062382364 cites W2029513681 @default.
- W2062382364 cites W2036656230 @default.
- W2062382364 cites W2040891489 @default.
- W2062382364 cites W2045697299 @default.
- W2062382364 cites W2047463168 @default.
- W2062382364 cites W2059443540 @default.
- W2062382364 cites W2066262976 @default.
- W2062382364 cites W2068656275 @default.
- W2062382364 cites W2069006374 @default.
- W2062382364 cites W2082842315 @default.
- W2062382364 cites W2086132101 @default.
- W2062382364 cites W2086735305 @default.
- W2062382364 cites W2090262385 @default.
- W2062382364 cites W2091324318 @default.
- W2062382364 cites W2091765696 @default.
- W2062382364 cites W2098107787 @default.
- W2062382364 cites W2117894566 @default.
- W2062382364 cites W2121776936 @default.
- W2062382364 cites W2127153704 @default.
- W2062382364 cites W2131324701 @default.
- W2062382364 cites W2140740752 @default.
- W2062382364 cites W2166677587 @default.
- W2062382364 cites W2951084511 @default.
- W2062382364 cites W2951238970 @default.
- W2062382364 cites W2951432566 @default.
- W2062382364 cites W2951809613 @default.
- W2062382364 cites W2951973683 @default.
- W2062382364 cites W3023905201 @default.
- W2062382364 doi "https://doi.org/10.1021/ja001184k" @default.
- W2062382364 hasPublicationYear "2000" @default.
- W2062382364 type Work @default.
- W2062382364 sameAs 2062382364 @default.
- W2062382364 citedByCount "70" @default.
- W2062382364 countsByYear W20623823642012 @default.
- W2062382364 countsByYear W20623823642013 @default.
- W2062382364 countsByYear W20623823642015 @default.
- W2062382364 countsByYear W20623823642018 @default.
- W2062382364 countsByYear W20623823642019 @default.
- W2062382364 countsByYear W20623823642020 @default.
- W2062382364 countsByYear W20623823642022 @default.
- W2062382364 crossrefType "journal-article" @default.
- W2062382364 hasAuthorship W2062382364A5003289867 @default.
- W2062382364 hasAuthorship W2062382364A5021271650 @default.
- W2062382364 hasAuthorship W2062382364A5047937683 @default.
- W2062382364 hasAuthorship W2062382364A5048985028 @default.
- W2062382364 hasAuthorship W2062382364A5061078135 @default.
- W2062382364 hasAuthorship W2062382364A5063906638 @default.
- W2062382364 hasAuthorship W2062382364A5072216093 @default.
- W2062382364 hasAuthorship W2062382364A5091872913 @default.
- W2062382364 hasConcept C106159729 @default.
- W2062382364 hasConcept C111771559 @default.
- W2062382364 hasConcept C120665830 @default.
- W2062382364 hasConcept C121332964 @default.
- W2062382364 hasConcept C13472781 @default.
- W2062382364 hasConcept C145148216 @default.
- W2062382364 hasConcept C147597530 @default.
- W2062382364 hasConcept C148898269 @default.
- W2062382364 hasConcept C152365726 @default.
- W2062382364 hasConcept C155647269 @default.
- W2062382364 hasConcept C158355884 @default.
- W2062382364 hasConcept C162324750 @default.
- W2062382364 hasConcept C178790620 @default.
- W2062382364 hasConcept C185592680 @default.
- W2062382364 hasConcept C2778689049 @default.
- W2062382364 hasConcept C54582936 @default.
- W2062382364 hasConcept C62520636 @default.
- W2062382364 hasConcept C70050531 @default.
- W2062382364 hasConcept C75473681 @default.
- W2062382364 hasConcept C93391505 @default.
- W2062382364 hasConceptScore W2062382364C106159729 @default.
- W2062382364 hasConceptScore W2062382364C111771559 @default.
- W2062382364 hasConceptScore W2062382364C120665830 @default.
- W2062382364 hasConceptScore W2062382364C121332964 @default.
- W2062382364 hasConceptScore W2062382364C13472781 @default.