Nitrosonium Research Articles

Transition-metal derivatives of arenediazonium ions. Part 8. The reactions of nitrosonium and arenediazonium ions with 2,2′-bipyridyl and 1,10-phenanthroline derivatives of Group 6 metal carbonyls

The reaction between [W(CO)4(phen)](phen = 1,10-phenanthroline) and [NO][PF6] in methanol–toluene gives mer-[W(CO)3(phen)(NO)][PF6](1) whereas [Mo(CO)4(L–L)][L–L = bipy (2,2′-bipyridyl) or phen] reacts with either [NO]+ or [RN2]+(R = aryl) in acetone to produce fac-[M(CO)3(L–L)Z][BF4][Z = NO (2) or RN2(3)]. The complexes [Mo(CO)3(L–L)(PPh3)] and either [NO]+ or [RN2]+ in acetone give [M(CO)2(L–L)Z(PPh3)]+[Z = NO (4) or RN2(5)] which may also be prepared form (1)–(3) and PPh3. With an excess of PPh3, (2) or (3) yield [Mo(CO)Z(L–L)(PPh3)2]+[Z = NO (6) or RN2(7)], and with halide ion (1)–(5) afford [MX(CO)2(L–L)Z][X = Cl, Br, or I; Z = NO (8) or RN2(9)]. Iodine or Br2, reacts with (5) to give [{MoX3(L–L)(N2R)}n](10; X = I or Br). On refluxing (1) in acetone, rapid partial hydrolysis of he [PF6]– anion, and carbonyl substitution, gives [W(CO)2(phen)(NO)(O2PF2)](11).

Acid-catalysed replacement of nitro-ligand from some dinitrodiamine platinum(II) complexes in acetic acid solutions

The replacement of nitro-ligand from the series of complexes, cis or trans [PtA 2(NO 2) 2] (where A = pyridine, NH 3 or PEt 3) in acetic acid solutions, has been studied. The results are compared with those previously reported for aqueous solutions. Added water retards the reactions. The mechanism suggested is one involving the loss of nitrosonium ion from the protonated species. Attempts to observe a species containing a platinum-proton linkage were unsuccessful.

Reactions of the nitrosonium ion. 10. Decarboxylations of azodicarboxylates by nitrosonium and nitronium salts. Decarboxylative oxidation and substitution reactions

Reactions of the nitrosonium ion. 10. Decarboxylations of azodicarboxylates by nitrosonium and nitronium salts. Decarboxylative oxidation and substitution reactions

The high pressure nitric oxide mass spectra of aldehydes

AbstractThe high pressure (0.5 Torr) nitric oxide mass spectra of some aldehydes, obtained using a 10% mixture of NO in N2, are reported. The 10% NO/N2 spectra of the monodeuterated analogs of some of them are compared to the electron‐impact and methane chemical ionization spectra, especially with reference to the process of hydride abstraction by nitrosonium ions.

Reactions of the nitrosonium ion. VIII. Reactions of nitrosonium tetrafluoroborate and benzhydryl tetrafluoroborate with benzhydryl azides. Mechanism of aldehyde and ketone formation

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTReactions of the nitrosonium ion. VIII. Reactions of nitrosonium tetrafluoroborate and benzhydryl tetrafluoroborate with benzhydryl azides. Mechanism of aldehyde and ketone formationMichael P. Doyle, David M. Hedstrand, Stanley C. Busman, and David AlexanderCite this: J. Am. Chem. Soc. 1975, 97, 19, 5554–5558Publication Date (Print):September 1, 1975Publication History Published online1 May 2002Published inissue 1 September 1975https://doi.org/10.1021/ja00852a039RIGHTS & PERMISSIONSArticle Views291Altmetric-Citations3LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (634 KB) Get e-Alerts Get e-Alerts

Reactions of the nitrosonium ion. VII. Syntheses of dihydroisoquinolines and oxazoles from azides in nitrile solvents

AbstractN‐Alkylnitrilium salts are cleanly produced from alkyl azides by reaction with nitrosonium salts in nitrile solvents. Syntheses of 3,4‐dihydroisoquinolines from nitrilium ions formed in this method from 2‐phenylethyl azide are described. Oxazoles are readily formed from phenacyl azides by this general method; the advantages of oxazole syntheses through azide nitrosation are discussed.

Kinetics and equilibria of the S-nitrosation of alkylthioureas

The equilibrium constants for the addition of the nitrosonium ion to the sulphur atom of a range of alkylthioureas have been measured, and shown to correlate well with the ionisation constants of the corresponding conjugate acids. Stopped-flow studies of the rate of reaction show it to occur by an encounter-controlled process.

Synthesen der Nonactinsäure

AbstractTwo stereoselective syntheses of nonactic acid I, the building block of the macrotetrolide antibiotic nonactin are described. The characteristic cis‐configuration of the 2,5‐substituents on the tetrahydrofuran ring of I is obtained in the first synthesis by catalytic hydrogenation of the furan derivative X. This key intermediate possesses the carbon skeleton and correct distribution of oxygen functions for conversin into nonactic acid. It is synthesized by an electrophilic substitution of 2‐acetonylfuran (VI) with the N‐cyclohexyl‐N‐propenyl nitrosonium ion (V) generated from the corresponding α‐chloronitrone (VII) and silver fluoroborate, followed by hydrolysis and oxidation of the aldehyde group.The second synthesis starts with a diol already having the correct configuration of the side chain that contains the hydroxyl group. For this purpose threo‐1‐octen‐5,7‐diol (XV) is synthesized from acetylacetone in two steps. Oxidative cleavage of the terminal double bond of this threo‐diol yields an aldehyde which is converted by a Wittig reaction, with the carbanion, obtained from diethyl α‐methoxycarbonylethyl phosphonate, into the open chain intermediate, 2‐methyl‐6,8‐dihydroxy‐2‐nonenoic acid methylester (XVIII). Base‐catalyzed cyclisation of this α,β‐unsaturated dihydroxy ester yields the methyl ester of nonactic acid (I) as the main product.

Addition of nitrosonium ion to mercaptide-bridged binuclear iron(II) and cobalt(II) complexes

Addition of nitrosonium ion to mercaptide-bridged binuclear iron(II) and cobalt(II) complexes

Phosphorus in Organic Synthesis. I. A New Method for the Preparation of Amides, Carbamates, Esters, and Carbonates by the Reaction of Alkylidenephosphoranes with Nitrosonium Ion

Some amides and carbamates, or some esters and carbonates were synthesized by the reaction of phosphoranes Ph3P=CHCOR (R=Me, Ph, OMe, OEt) with nitrosonium ion in the presence of some amines or alcohols.

Reactions of the nitrosonium ion. V. Nitrosative cleavage of the carbon-nitrogen double bond. Attempted exchange of oxygen for nitrogen

Reactions of the nitrosonium ion. V. Nitrosative cleavage of the carbon-nitrogen double bond. Attempted exchange of oxygen for nitrogen

ChemInform Abstract: N,N‐DIALKYL‐N‐OXO‐AMMONIUM‐SALZE

AbstractDurch Oxidation des Radikals (I) mit Antimonpentachlorid in Tetrachlorkohlenstoff bei ‐15°C erhält man das Salz (II) als gelben Niederschlag (Ausbeute 98%).

Oxidation of cellulose by acid‐sodium nitrite systems

AbstractInvestigations on the oxidation of cellulose by phosphoric acid‐sodium nitrite systems have shown that the specificity of the reaction depends on the concentration of the acid. Supporting evidence has been given by chemical analysis, x‐ray diagrams, and identification of degradation products. The suggestion of a mechanism of oxidation by the nitrosonium ion instead of nitrous acid is supported by experimental results.

The electrochemical reduction of nitrosonium ion in concentrated sulphuric acid: The NO +/NO redox couple

The electrochemical reduction of NO + ion in concentrated sulphuric acid has been studied on gold and platinum electrodes in the temperature range from 4·5 to 55·5°C with the rotating disk electrode, linear potential-sweep voltammetry and chronopotentiometry. On gold, NO + is reduced to NO, the reaction being a reversible one-electron transfer reaction. The experimental diffusion coefficients of the NO + ion and NO molecule are evaluated. On platinum, in the potential region where reduction of NO + ion and oxidation of NO occur, oxides formed on the metal interfere, thus making the interpretation of the process difficult.

Reactions of NO+ with H2O in a Photoionization Mass Spectrometer

The reactions of NO+ with H2O have been studied in a photoionization mass spectrometer. Nitrosonium ions produced by Kr resonance radiation at 10.03 eV react with water in a field free region. Products observed are NO(H2O)n+ (n=1, 2, 3) and H(H2O)n+ (n=1–5). Rate constants are calculated, heats of formation of hydrated NO+ are estimated and some evidence is presented which is consistent with a structure of NO(H2O)n+ where the waters are hydrogen bonded in a linear fashion rather than forming a solvation sphere.

The nitrosonium ion, NO +, and its versatility in transition metal organometallic synthesis

The versatility of the nitrosonium ion, NO +, in organometallic synthesis is illustrated by its reactions with a variety of transition metal compounds. With the species π-C 5H 5M(CO)P(C 6H 5) 3, MCo and Rh, NOPF 6 reacts in methanol/toluene mixtures to give [π-C 5H 5M(NO)P(C 6H 5) 3]PF 6. When MIr, however, protonation takes place to give the hydride [π-C 5H 5Ir(CO)P(C 6H 5) 3H]PF 6. Halogen-containing organometallics such as π-C 5H 5Fe(CO) 2I, (π-C 5H 5) 2VCl 2 and Mn(CO) 5Br react with NOPF 6 in acetonitrile to give the complexes [π-C 5H 5Fe(CO) 2(CH 3CN)]PF 6, [(π-C 5H 5) 2V(CH 3CN) 2][PF 6] 2 and [Mn(CO) 5(CH 3CN)]PF 6 in which the solvent has replaced the halide ligands. Finally NO + reacts as a one-electron oxidising agent towards (π-C 5H 5) 2Fe and [π-C 5H 5Fe(CO)SCH 3] 2 giving (π-C 5H 5) 2Fe + and [π-C 5H 5Fe(CO)SCH 3] 2 + respectively. Reasons for the formation of the different types of products are discussed.

Reactions of the nitrosonium ion. III. Reaction of alkyl azides with nitrosonium compounds. Effect of solvent, quenching agent, and nitrosonium compound

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTReactions of the nitrosonium ion. III. Reaction of alkyl azides with nitrosonium compounds. Effect of solvent, quenching agent, and nitrosonium compoundMichael P. Doyle and Wendell WierengaCite this: J. Am. Chem. Soc. 1972, 94, 11, 3901–3906Publication Date (Print):May 1, 1972Publication History Published online1 May 2002Published inissue 1 May 1972https://doi.org/10.1021/ja00766a040RIGHTS & PERMISSIONSArticle Views194Altmetric-Citations3LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (751 KB) Get e-Alerts Get e-Alerts

Reactions of the nitrosonium ion. IV. Nitrosative cleavage of the carbon-nitrogen double bond. Reaction of N-arylimines and ketimines with nitrosonium salts

Reactions of the nitrosonium ion. IV. Nitrosative cleavage of the carbon-nitrogen double bond. Reaction of N-arylimines and ketimines with nitrosonium salts

Reactions of the nitrosonium ion. II. Reactions of triphenylmethyl, benzhydryl, and benzyl azides with nitrosonium compounds

Reactions of the nitrosonium ion. II. Reactions of triphenylmethyl, benzhydryl, and benzyl azides with nitrosonium compounds

Nitration of Durene and Pentamethylbenzene with Nitronium Salts in Nitromethane and Acetonitrile

AbstractNature and proportions of the products formed in the nitrations mentioned in the title are affected by the process of mixing.Pentamethylnitrobenzene, formed initially in the nitration of pentamethylbenzene, is attacked by a nitronium ion at a position meta to the nitro‐group. In the σ‐complex formed, loss of a proton from a methyl group leads to production of by‐products and release of nitrite ions. The nitrous acid formed is protonated, and water is displaced from the nitrous acidium ion by the anion, PF6⊖, giving the nitrosonium ion which forms a 1:1 symmetric molecular complex with pentamethylbenzene. A similar complex is formed in the reaction between durene and nitronium salts.The results are consistent with the view that no σ‐bond is formed between the aromatic compound and the nitrosonium ion.