Reactions of alkoxy radicals with O2. I. C2H5O radicals

C₂H₅ONO was photolyzed with 366 nm radiation at ?48, ?22, ?2.5, 23, 55, 88, and 120°C in a static system in the presence of NO, O₂, and N₂. The quantum yield of CH₃CHO, Φ{CH₃CHO}, was measured as a function of reaction conditions. The primary photochemical act is and it proceeds with a quantum yield ?_1a = 0.29 ± 0.03 independent of temperature. The C₂H₅O radicals can react with NO by two routes The C₂H₅O radical can also react with O₂ via Values of k₆/k₂ were determined at each temperature. They fit the Arrhenius expression: Log(k₆/k₂) = ?2.17 ± 0.14 ? (924 ± 94)/2.303 T. For k₂ ? 4.4 × 10^?11 cm³/s, k₆ becomes (3.0 ± 1.0) × 10^?13 exp{?(924 ± 94)/T} cm³/s. The reaction scheme also provides k_8a/k₈ = 0.43 ± 0.13, where      

Reactions of Cyclopalladated Benzylidene-aniline Schiff's Base Complexes. Selective Synthesis of 2′-Substituted Schiff's Base Derivatives and the X-Ray Crystal Structure of the Dimer [Pd(μ-OAc)(5′-OCH3?C6H3CHNC6H4-4-CH3)]2

The 2′-cyclopalladated imine complex , reacts with CO in MeOH to afford the 2′-substituted aryl imine 2′-CO₂CH₃-5′-OCH₃? C₆H₃CH?NTol (Tol = C₆H₄-4-CH₃). The product of this reaction can be altered by changing the bridging ligand from AcO to Cl, in which case only the 5-membered ring heterocyclic compound is obtained. [Pd(μ-OAc)( 1a )]₂ with 2 equiv. of Ph₃P and CO (1 atm) gives the heterocyclic which arises from two CO insertion reactions, whereas [PdX( 1a )]₂ (X = AcO, Cl) with 4 equiv. of C?NBu^t and 4 equiv. of Ph₂PCH₂CH₂PPh₂ affords the heterocyclic ketenimine [PdCl( 1a )]₂ reacts with CH₂?CHCO₂CH₂CH₃ to afford 2′(? CH?CHCO₂CH₂CH₃)-5′-OCH₃C₆H₃CHO, and [Pd(μ-OAc)( 1a )]₂ with I₂ to give 2′-I-5′-OCH₃C₆H₃CHO. Excess CH₃O₂CC?CCO₂CH₃ reacts with various substituted cyclopalladated Schiff's bases in MeOH to afford which we formulate as possessing two Pd? C bonds, and one coordinated ester O atom. The X-ray crystal structure of [Pd(μ-OAc)( 1a )]₂ has been determined; relevant bond lengths [Å] and bond angles [°] are: Pd? O(1), 2.139(6), Pd? O(2), 2.026(6), Pd? N, 2.039(6), Pd? C(2′), 1.951(8), Pd? Pd, 3.113(1), N? Pd? C(2′), 80.9(3), N? Pd? O(1), 97.5(2), C(2′)? Pd? O(2), 91.7(3), O(1)? Pd? O(2), 89.2(2).     

Fluorierung von Dioxa- und Oxazaphospholanen

Fluorination of Dioxa- and Oxazaphospholanes The fluoridolysis of cyclic esters and esteramides of phosphorous acid ( 1 , 2 , 4 , 5 , 7 , 11 , and 12 ,) using the acid fluorination reagent Et₃N · nHF (n > 1) or an excess of a basic composed agent (n < 1) yields in all cases HPF₅^? ( 3 ,). With stoichiometric amounts of fluoride, however, the fluorophospholanes ( 4 ,) and ( 5 ,) as well as fac.- and mer.-o- ( 6a, 6b ,) and the spirocyclic fluorohydridophosphate ( 8 ,) are obtained. ( 13 ,) reacts to ( 14 ,) and the spirocyclic compound ( 15 ,) gives ( 16 ,). The fluorophosphoranes ( 18 ,), ( 19 ,), and ( 21 ,) are obtained by oxidative fluorination of the spiro- or bicyclic P? H compounds 11, 12 , and 20 , with CCl₄/Et₃N · nHF (n < 1). The oxidative fluorination of the cyclic triesters of phosphorous acid 7 , and 23 , leads to the cyclic fluorophosphates ( 22 ,) and 16 , as well as 6. , The compounds 18, 19 , and 22 , are also formed by oxidative fluorination of elemental phosphorus, P₄, in the presence of the corresponding bifunctional nucleophile.     

Beiträge zur Komplexchemie der Phosphine und Phosphinoxide,XXVIII. Übergangsmetall-aminoalkylphosphin-Komplexe Teil 2: Palladium- Und Platinkomplexe

On the Coordination Chemistry of Phosphines and Phosphine Oxides. XXVIII. Transition Metal Aminoalkylphosphine Complexes. Part II: Palladium and Platinum Complexes Aminoalkylphosphines – C₆H₅HP? CH₂ · CH₂? , (C₆H₅)₂P? CH₂ · CH₂ · CH₂? NH₂, (C₆H₅)₂P? CH₂ · CH₂ · CH₂? N?CHC₆H₅ – react with palladium and platinum salts to give coordination compounds of the type MX₂, MX₂()₂, and MX₂()₄ (M = Pd, Pt; X = Cl, BPh₄). The chelating activity of the ligands, structure and properties of the metal complexes are discussed.     

Perfluorovinyl Morpholine and Perfluorovinyl Pyrrolidine with Nucleophiles and Electrophiles

In this study, both monofunctional and bifunctional nucleophiles, as well as the electrophile FNO, are reacted with perfluorovinyl amines. The perfluorovinyl amines CF?CF₂ and CF?CF₂ have been reacted with dimethylamine and diethylamine in the presence of small amounts of water to give CHFC(O)N(CH₃)₂ ( 1 ), CHFC(O)N(CH₃)₂ ( 2 ), and CHFC(O)N(C₂H₅)₂ ( 3 ). With perfluorovinyl pyrrolidine and perfluorovinyl morpholine, ethanolamine gives the cyclized products CHF ( 4 ) and CHF ( 5 ), respectively. Reaction of the vinyl amines with (CH₃)₃SiOCH₂CF₃ in the presence of catalytic amounts of CsF results in the formation of cis- ( 6 ) and trans- ( 7 ) CF?CF(OCH₂CF₃) and cis- ( 8 ) and trans- ( 9 ) CF?CF(OCH₂CF₃). The electrophile FNO reacts slowly with perfluorovinyl pyrrolidine and perfluorovinyl morpholine, and more rapidly with (CF₃)₃CCF?CF₂ to give CF(NO)CF₃ ( 10 ), CF(NO)CF₃ ( 11 ) and (CF₃)₃CF(NO)CF₃ ( 12 ), respectively. Single crystal X-ray analysis is used to confirm the identity of the product obtained from the controlled hydrolysis of the sultone of perfluorovinyl pyrrolidine as the sulfonic acid anhydride C(O)CF₂OS(O)₂OCF₂C(O) ( 13 ). The X-ray crystal structure of perfluorosuccinic acid monohydrate ( 14 ), which is obtained when the perfluorovinyl pyrrolidine sultone is hydrolyzed in excess water, is also reported for the first time.     

Trägerfixierte Organometallkomplexe. VI. Charakterisierung und Reaktivität Polysiloxan-gebundener (Ether-phosphan)ruthenium(II)-Komplexe

Supported Organometallic Complexes. VI. Characterization und Reactivity of Polysiloxane-Bound (Ether-phosphane)ruthenium(II) Complexes The ligands PhP(R)CH₂D [R = (CH₃O)₃Si(CH₂)₃; D = CH₂OCH₃ ( 1b ); D = tetrahydrofuryl ( 1c ); D = 1,4-dioxanyl ( 1d )] have been used to synthesize (ether-phosphane)ruthenium(II) complexes, which have been copolymerized with Si(OEt)₄ to yield polysiloxane-bound complexes. The monomers cis,cis,trans-Cl₂Ru(CO)₂(P ～ O)₂ ( 3b ) and HRuCl(CO)(P ～ O)₃ ( 5b ) were treated with NaBH₄ to form cis,cis,trans-H₂Ru(CO)₂(P ～ O)₂ ( 4b ) and H₂Ru(CO)(P ～ O)₃ ( 6b ), respectively (P ～ O = η¹-P coordinated; = η²- coordinated). Addition of Si(OEt)₄ and water leads to a base catalyzed hydrolysis of the silicon alkoxy-functions and a precipitation of the immobilized counterparts 4b ′, 6b ′. The polysiloxane matrix resulting by this new sol gel route has been described under quantitative aspects by ²⁹Si CP-MAS NMR spectroscopy. 4b ′ reacts with carbon monoxide to form Ru(CO)₃(P ～ O)₂ ( 7b ′). Chelated polysiloxane-bound complexes Cl₂Ru( )₂ ( 9c ′, d ′) and Cl₂Ru( )(P ～ O)₂ ( 10b ′, c ′) have been synthesized by the reaction of 1b–c with Cl₂Ru(PPh₃)₃ ( 8 ) followed by a copolymerization with Si(OEt)₄. The polysiloxane-bound complexes 9c ′, d ′ and 10b ′, c ′ react with one equivalent of CO to give Cl₂Ru(CO)( )(P ～ O) ( 12b ′– d ′). Excess CO leads to the all-trans-complexes Cl₂Ru(CO)₂(P ～ O)₂ ( 14b ′– d ′), which are thermally isomerized to cis,cis,trans- 3b ′– d ′. The chemical shift anisotropy of ³¹P in crystalline Cl₂Ru( )₂ ( 9a , R = Ph, D = CH₂OCH₃) has been compared with polysiloxane-bound 9d ′ indicating a non-rigid behavior of the complexes in the matrix.     

Synthese und spektroskopische Charakterisierung einiger Pentacarbonylwolfram(0)-Komplexe mit verschiedenen 1H-Phosphiren-Liganden,Kristallstrukturen von,und

Synthesis and Spectroscopic Characterization of some Pentacarbonyltungsten(0) Complexes with Various 1H-Phosphirene Ligands: Crystal Structures of , and The tungsten(0) complex 1 reacts upon heating with acetylene derivatives 2a–f in toluene to form benzonitrile and the complexes 4a–f ( 4a : R¹ ? Ph, R² ? H; 4b : R¹ ? Ph, R² ? CH₃; 4c : R¹ ? OEt, R² ? H; 4d : R¹ ? Ph, R² ? CO₂Et; 4e : R¹, R² ? CO₂Me; 4f : R¹, R² ? SiMe₃), which have been isolated by chromatography. Spectroscopic and mass spectrometric data are discussed. The crystal structures of the compounds 4a, b and d were determined by X-ray single crystal structure analysis ( 4a : space group P2₁/n, Z = 4, a = 937,5(2) pm, b = 2202,4(6) pm, c = 1266,3(4) pm, β = 108,94(4)°; 4b : space group P2₁/c, Z = 4, a = 1293,9(2) pm, b = 923,5(1) pm, c = 2223,4(3) pm, β = 92,385(6)°; 4d : space group P2₁/c, Z = 4, a = 955,2(2) pm, b = 3190,9(4) pm, c = 930,7(2) pm, β = 99,64(1)°).     

Über die oxidative Fluorierung von (CF3)(R) (R = CF3, Cl) und die Kristallstruktur von (CF3)(Cl)F+ AsF6−

Oxidative Fluorination of (CF₃)(R) (R = CF₃, Cl) and the Crystal Structure of (CF₃)(Cl) F⁺ AsF₆^? Oxidative fluorination of (CF₃)(R) (R = CF₃, Cl) with XeF⁺MF₆^? (M = As, Sb) in anhydrous HF results in formation of monofluorsulfonium hexafluorometalates. The salts are characterized by vibrational, NMR, and mass spectra. (CF₃)(Cl)F⁺ AsF₆^? crystallizes in the monoclinic space group P2₁/c with a = 9.955(10) Å, b = 11.050(5) Å, c = 12.733(15) Å, β = 97.77(5)°, and Z = 4.     

The gas phase ion chemistry of the acetyl cation and isomeric [C2H3O]+ ions. On the structure of the [C2H3O]+ daughter ions generated from the enol of acetone radical cation

Methods are described for the unequivocal identification of the acetyl, [CH₃? \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm C}\limits^{\rm + } $\end{document} ?O] (a), 1-hydroxyvinyl, [CH₂?\documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm C}\limits^{\rm + } $\end{document}? OH] (b), and oxiranyl, (d), cations. They involve the careful examination of metastable peak intensities and shapes and collision induced processes at very low, high and intermediate collision gas pressures. It will be shown that each [C₂H₃O]⁺ ion produces a unique metastable peak for the fragmentation [C₂H₃O]⁺ → [CH₃]⁺+CO, each appropriately relating to different [C₂H₃O]⁺ structures. [CH₃? \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm C}\limits^{\rm + } $\end{document}?O] ions do not interconvert with any of the other [C₂H₃O]⁺ ions prior to loss of CO, but deuterium and ¹³C labelling experiments established that [CH₂?\documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm C}\limits^{\rm + } $\end{document}? OH] (b) rearranges via a 1,2-H shift into energy-rich leading to the loss of positional identity of the carbon atoms in ions (b). Fragmentation of b to [CH₃]⁺+CO has a high activation energy, c. 400 kJ mol^?1. On the other hand, , generated at its threshold from a suitable precursor molecule, does not rearrange into [CH₂?\documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm C}\limits^{\rm + } $\end{document}? OH], but undergoes a slow isomerization into [CH₃? \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm C}\limits^{\rm + } $\end{document}?O] via [CH₂\documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm C}\limits^{\rm + } $\end{document}HO]. Interpretation of results rests in part upon recent ab initio calculations. The methods described in this paper permit the identification of reactions that have hitherto lain unsuspected: for example, many of the ionized molecules of type CH₃COR examined in this work produce [CH₂?\documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm C}\limits^{\rm + } $\end{document}? OH] ions in addition to [CH₃? \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm C}\limits^{\rm + } $\end{document}?O] showing that some enolization takes place prior to fragmentation. Furthermore, ionized ethanol generates a, b and d ions. We have also applied the methods for identification of daughter ions in systems of current interest. The loss of OH^˙ from [CH₃COOD]^+˙ generates only [CH₂?\documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm C}\limits^{\rm + } $\end{document}? OD]. Elimination of CH₃^˙ from the enol of acetone radical cation most probably generates only [CH₃? \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm C}\limits^{\rm + } $\end{document}?O] ions, confirming the earlier proposal for non-ergodic behaviour of this system. We stress, however, that until all stable isomeric species (such as [CH₃? \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm O}\limits^{\rm + } $\end{document}?C:]) have been experimentally identified, the hypothesis of incompletely randomized energy should be used with reserve.     

Silaethene. III. Versuche zur Darstellung und spektroskopischen Charakterisierung von H2SiCH2, D2SiCH2 und Me(H)SiCH2

Silaethenes. III. Preparation and Spectroscopic Characterization of H₂Si?CH₂, D₂Si?CH₂, and Me(H)Si?CH₂ H₂Si?CH₂ and D₂Si?CH₂ are formed together with ethene and propene by gas phase pyrolysis at low pressure (10^?2–10^?3 mbar) from the corresponding mono- or 1,3-disilacyclobutanes in good yield and are characterized by i.r. and mass spectroscopic methods. Formation of propene can be explained by following reactions of the silaethene intermediate using a “head-to-head” mechanism. H₂Si?CH₂ can be stored at ?196°C for several months and can be transferred by trap-to-trap distillation in a vacuum system. Similar results are obtained for .     

Darstellung,Eigenschaften sowie Reaktionen metallhaltiger Heterocyclen. LXVI. Nickelinduzierte Cyclocodimerisierung eines Thioxophosphor(V)-Kations mit einem aktivierten Alkin

Metall Containing Heterocycles: Preparation, Properties, Reactions. LXVI. Nickel Induced Cyclocodimerization of a Thioxophosphorus (V) Cation with an Activated Alkyne The action of di-tert-butylthioxophosphorane (t-Bu)₂P(H)S on nickelocene in ether results in the formation of the first kinetically stabilized (η²-diorganothioxophosphorus)nickel complex [(η⁵-C₅H₅)Ni(η²-S?P(t-Bu)₂)] ( 1 ). In presence of the acetylene dicarboxylic acid dimethyl ester H₃CO₂CC? CCO₂CH₃ with (t-Bu)₂P?S a cyclocodimerization occurs with formation of the S and P isomeric thiaphosphanickelacyclopentadiene (η⁵-C₅H₅) ( 2S ) and thiaphosphanickelacyclopentene (η⁵-C₅H₅) ( 2P ) (R?CO₂CH₃), respectively. The composition and structure of the compounds 1, 2S , and 2P were determined from the mass, IR, and NMR spectra.     

Computer-simulated ESR spectra of irradiated poly(olefin oxides)—effect of glass transition temperature on the ESR spectra

Investigations on the effects of γ irradiation on poly(methylene oxide) (POM) and poly(ethylene oxide) (PEO) have been made employing electron spin resonance (ESR) spectroscopy. The ESR sextet and doublet spectra, recorded for POM and PEO, respectively, on irradition in air at room temperature are broadened as the temperature is lowered and show a reversible change in line shape with temperature. The spectra are analyzed by computer simulation, employing Lorentzian line-shape functions and the least-squares method of total curve fitting. The component spectra are evaluated and are assigned. Superposition of the component quartet, triplet, and doublet spectra, corresponding to the radicals ?H₃, ?H₂O , and O?HO , respectively, together with a singlet due to the radicals ?CH₂ is considered to be the best fit to the observed spectrum for POM. The doublet spectrum recorded for PEO has been assigned to the radicals ?HO . The reversible broadening of the spectra has been associated with the mechanism of molecular motions around the glass transition temperatures of these polymers.     

Zur Reaktivität isomerer Heterodinuclearer Fischer-Carben-Komplexe mit Titanaoxetan- und Titanaoxolenteilstrukturen — Cycloreversions- und Insertionsreaktionen

Studies on the Reactivity of Isomeric Heterodinuclear Fischer-Carbene Complexes exhibiting a Titanaoxetan or Titanaoxolen Substructure – Cycloreversion and Insertion Reactions The reactivity of isomeric four- and five-membered carbene complexes Cp*₂ 3 and Cp*₂ 4 [ML_n: Cr(CO)₅ ( a ); W(CO)₅ ( b ); Cp*: C₅(CH₃)₅] has been investigated. A cycloreversion reaction, unusual for common metallaoxetanes, is found to dominate the chemical behaviour of 3 . The generation of vinylidene fragment [Cp*₂Ti?C?CH₂] 2 as an intermediate is proved either by trapping with ethylene and isocyanate or by protonation of the α-carbon atom. On the other hand no cycloreversion is observed for the titanaoxolene carbene complexes 4 . Ringenlargement is found by the reaction of 3 and 4 with isonitriles under formation of iminoacyl complexes. Accordingly 2,6-dimethylphenylisonitrile reacts with 3 b forming Cp*₂ 12 [Ar: 2,6-(CH₃)₂? C₆H₃]. A reversible insertion of cyclohexylisonitrile in 4a leads to isolation of the six-membered metallacycle Cp*₂ 16 (Cy: C₆H₁₁).     

Kinetics of the bromine catalyzed elimination of HCl from 1,1,1-trichloroethane

The gas phase kinetics of the bromine catalyzed elimination of HCl from 1,1,1-trichloroethane has been studied over a five fold variation of (CH₃CCl₃)/(Br₂) and from 565 to 634 K. The most important reactions in the mechanism are found to be: The preferred analysis of the kinetic data results in log(k₁/M^?1 s^?1) = 11.3 ± 0.3 ? (19.9 ± 1.0) × 10³/4.575 T. From these results one calculates the C—H bond dissociation energy in CH₃CCl₃ to be 103.8 ± 2 kcal mol^?1, and the heat of formation of 2,2,2-trichloroethyl to be 17.7 ± 2 kcal mol^?1.     

Zur Reaktion der Lewis-Base [Mn(CO)5]− mit Donor/ Akzeptor-Liganden des Typs Me2PCH2CH2SiX3 (X = F,Cl, OMe)

Alternative Ligands. XVII. Reaction of the Lewis Base [Mn(CO)₅]^? with Donor/Acceptor Ligands Me₂PCH₂CH₂SiX₃ (X = Cl, F, OMe) Reactions [eqn. (1) and (2)] for the preparation of intramolecular adducts between the base [Mn(CO)₄PMe₂R]^? and the Lewis acidic terminal group SiX₃ of the ligands Me₂PCH₂CH₂SiX₃ (X = Cl, F, OMe) have been studied. Cleavage of the MnSi bond with Cl^? [equ.(2)] in the chelate complex to form the complex salt [Ph₄As][Mn(CO)₄PMe₂ CH₂CH₂SiCl₃] proves unsuccessful because of the surprising stability of this bond. The alternative route [equ. (1)] yields the anionic species [Mn(CO)₄PMe₂CH₂CH₂SiX₃]^? in the first step, but reaction conditions favour the formation of with decreasing tendency Cl> F> OMe. The complex salts, therefore, cannot be isolated as pure compounds.     

Darstellung und Eigenschaften von N,N-Dialkyl-allylaminoboran-Addukten und N,N-Dimethyl-aminopropylboran

Synthesis and Properties of N,N-Dialkyl-allylaminoboranes and N,N-Dimethylaminopropylborane Complexes of the type H₃B ← NR₂(CH₂CH?CH₂) (R?CH₃ I , C₂H₅ II ) are formed by reaction of Li[BH₄] with dialkylallylammonium salts. By addition of AlCl₃ I can be transformed into the chelate-stabilized N,N-dimethyl-aminopropylborane III . The i.r.-, ¹H, ¹³C-n.m.r. and mass-spectra of I – III are reported and discussed.     

Sulfoximid und Sulfoximidium-Salze – Strukturen und H?Brückenbindungen

Sulfoximide and Sulfoximidium Salts – Structures and Hydrogen Bonding In the solid state dimethylsulfoximide ( 1 ) (orthorhombic; space group Pbca; a = 577.8, b = 931.2 and c = 1645.6 pm) makes intermolecular N? H ? N hydrogen bonds. The hydrogen halide salts (CH₃)₂S(O)NH₂⁺Hal^? (( 2 ), Hal^??Cl^?; ( 4 ), Hal^??Br^?) reacts with metal halides to yield (CH₃)₂S(O)NH₂⁺MHal with the complex anions (( 5 ), MHal?SbCl₄^?; ( 6 ), MHal?SbCl₅^2?; ( 7 ), MHal?SbCl₆^?; ( 8 ), MHal?SbBr₅^2?; ( 9 ), MHal?AlCl₄^?). 2 crystallizes from ethanol (96%) as [(CH₃)₂S(O)NH₂⁺Cl^?]₂ · H₂O ( 3 ). The structures of 3 (monoclinic; space group P2₁/c; a = 917.0, b = 1344.7, c = 1080.8 pm and β = 103.8°; Z = 10), 4 (orthorhombic; space group Pbcn; a = 1028.9, b = 1132.6, c = 1074.1 pm; Z = 8) and 6 (monoclinic; space group C2/c; a = 2041.1, b = 1101.4, c = 3365.6 pm and β = 153.8°; Z = 8) are determined by X-ray analysis. In 6 Sb is coordinated in a distorted octahedra by 6 Cl in three short (mean 245,5 pm; SbCl₃) and three long distances (291 to 299 pm; Cl^?). Two of the chloride ions connect the Sb atoms to infinite Sb …? Cl …? Sb chains. Except for 7 and 9 there are bridges between the NH₂ groups and the halide ions. The NH valence vibrations are discussed in view of hydrogen bonding.     

Cluster ions in the secondary ion mass spectrometry of choline and acetylcholine halides

Liquid secondary ion mass spectra of choline and acetylcholine halides exhibit several series of cluster ions whose origins were investigated using B/E and B²/E linked-scan techniques. In the case of choline halides three series of cluster ions were identified as (Me₃$ \mathop {\rm N}\limits^ + $CH₂CH₂OH + nM), (Me₃$ \mathop {\rm N}\limits^ + $CH₂CH₂OMe + nM) and (Me₃N$ \mathop {\rm N}\limits^ + $CH₂CH₂OH · Me₃$ \mathop {\rm N}\limits^ + $CH₂CH₂O^? + nM), while (CH₃COOCH₂CH₂$ \mathop {\rm N}\limits^ + $Me₃ + nM), (Me₃$ \mathop {\rm N}\limits^ + $CH₂CH₂OH + nM) and (CH₂ = CH$ \mathop {\rm N}\limits^ + $Me₃ + nM) were observed in the spectra of acetylcholine halides. For these cluster ions, bimolecular reactions induced on ion bombardment under secondary ion mass spectrometric conditions are discussed.     

Kinetics and the mechanism of the thermal reaction between trifluoromethylhypofluorite and hexafluoropropene

The kinetics of the thermal reaction between CF₃OF and C₃F₆ have been investigated between 20 and 75°C. It is a homogeneous chain reaction of moderate length where the main product is a mixture of the two isomers 1-C₃F₇OCF₃ (68%) and 2-C₃F₇OCF₃ (32%). Equimolecular amounts of CF₃OOF₃ and C₆F₁₄ are formed in much smaller quantities. Inert gases and the reaction products have no influence on the reaction, whereas only small amounts of oxygen change the course of reaction and larger amounts produce explosions. The rate of reaction can be represented by eq. (I): The following mechanism explains the experimental results: Reaction (5) can be replaced by reactions (5a) and (5b), without changing the result: Reaction (4) is possibly a two-step reaction: For ∣CF₃ = ∣C₃F₆∣, ν_20°C = 36.8, ν_50°C = 24.0, and ν_70°C = 14.2.     

Kinetics and mechanism of the reaction H + CH3ONO

The reaction of hydrogen atoms with methyl nitrite was studied in a fast-flow system using photoionization mass spectrometry and excess atomic hydrogen. The associated bimolecular rate coefficient can be expressed by in the temperature range of 223-398°K. NO, CH₃OH, CH₄, C₂H₆, CH₂O, and H₂O are the main products; OH and CH₃ radicals were detectable intermediates. The mechanism was deduced from the observed product yields using normal and deuterated reactants. The primary reaction steps were identified as followed by a rapid unimolecular decomposition of CH₂ONO into CH₂O and NO. Since the extent of reaction channel (1b) could not be determined independently, only extreme limits could be obtained for the individual contributions of the two channels of reaction (3) which follows the generation of CH₃O radicals: The most probable values, k_3a/k₃ = 0.31 ± 0.30 and k_3b/k₃ = 0.69 ± 0.30, support the previous results on this reaction, although the range of uncertainties is much greater here.