Ferrocenyl Sulfinylimide and Diferrocenyl Sulfurdiimide,Fc?NSO and Fc(NSN)Fc

1 Abbreviations and Nomenclature: Fc = η¹-ferrocenyl, CpFe(C₅H₄-); Cp = η⁵-cyclopentadienyl, η⁵-C₅H₅. Compounds containing the —NSO group are designated as either thionylimides, sulfinylimides or N-sulfinylamines. The systematic name is imido oxo sulfuranes(IV).

The reactions of ferrocenylamine, Fc? NH₂ ( 1 ), with thionyl chloride and sulfur dichloride in hexane solution in the presence of triethylamine lead to the title compounds Fc? NSO ( 2 ) and Fc(NSN)Fc ( 3 ), respectively, 2 and 3 have also been obtained in reactions of the silylated ferrocenylamine, Fc? NH(SiMe₃) ( 1b ), with thionyl chloride. The ferrocenyl sulfinylimide 2 has been converted to sulfurdiimides such as Fc(NSN)Fc ( 3 ) and Fc(NSN)R (R = ^tBu ( 4a ), SiMe₃ ( 4b )) by reaction with the lithium derivative of silylated amines, LiN(SiMe₃)R (R = Fc, ^tBu, SiMe₃). The new ferrocenyl compounds 2–4 have been characterized by their NMR spectra, and their electrochemical behaviour has been studied. The molecular structure of Fc? NSO ( 2 ) has been determined by an X-ray structure analysis; the sulfinylimide has the Z configuration, and the —NSO group is coplanar with the cyclopentadienyl ring to which it is attached.     

The site of radical attack at the furan ring from MNDO calculations

The semi-empirical SCF MNDO method has been used to calculate the radical reactivities for each reaction site in some neutral furan molecules as the average of the HOMO and LUMO probabilities both in 2p_z atomic orbitals 1

1 SCF: Self-consistent field; MNDO: modified neglect of differential overlap; HOMO: highest occupied molecular orbital; LUMO: lowest unoccupied molecular orbital.

. The carbon atoms C⁵ and C² of of the furan ring are the most favoured sites except for the furan derivatives holding a double bond in the substituent group. Also the SOMO 2

2 SOMO: Single occupied molecular orbital.

probabilities of the radicals formed by addition of a hydrogen atom or a vinyl acetate model radical were calculated. Thus, once a radical is added to the C⁵ position the resulting radical can be partially localized on the carbon C². Furthermore, the enthalpy of reaction for several radicals was estimated by using the calculated heats of formation of the neutral furan molecules and their radicals. The radical addition to the carbon C ⁵ resulted in the most exothermic reaction in comparison with other reaction sites of the molecule. However, no correlation was found between the calculated enthalpies and the degradative-transfer kinetic constants experimentally determined for the radical polymerization of vinyl acetate in the presence of the furan compounds under study.     

Coupling of two phosphaalkynes via a carbonyl group in the addition across a rhrh double bond

Phosphaalkynes, RCP (R = Bu^t, Adamantyl), add across the RhRh double bond of [Rh₂Cpequation/tex2gif-stack-1.gif(CO)₂] to give either [Rh₂Cpequation/tex2gif-stack-2.gif(μ-CO)(COPCR)] or [Rh₂Cpequation/tex2gif-stack-3.gif(CO){PCRC(O)CRP}] depending on the stoichiometry of the reaction (Cp* = η⁵-C₅Me₅). The structures of these complexes have been elucidated by NMR spectroscopy and by a single crystal X-ray study on [Rh₂Cpequation/tex2gif-stack-4.gif(CO){PCAdC(O)CPAd}]. Small amounts of the 1,3-diphosphacyclobutadiene complexes [RhCp*(P₂C₂R₂)] and the trinuclear compound [Rh₃Cpequation/tex2gif-stack-5.gif(CO)₂] are also formed in these reactions. The reactions of RCP with [CoRhCp₂*(CO)₂] are also described.

1 A preliminary account of part of this work has appeared in J. Chem. Soc., Chem. Commun., 1987, 658.

     

Anion‐aided Dynamic One‐pot Self‐assembly of Rectangular Metallacycles

The tetracopper(I) complex [{Cu₂(μ‐dppm)₂}₂(μ‐1,4‐O₂CC₆H₄ (CO₂ )₂)](BF₄ )₂ ( 1 (BF₄ )₂) and 1,2‐bis(4‐pyridyl)ethane (bpa) can establish a dynamic equilibrium in CH₂Cl₂ . From the equilibrium mixture containing 1 (BF₄ )₂ and bpa with the molar ratio 1 (BF₄ )₂/bpa of 1:1, a supramolecular compound [{Cu₂(μ‐dppm)₂}₂(μ‐1,4‐C₆H₄ (CO₂ )₂)(μ‐bpa)]₂(BF₄ )₄ ( 2 (BF₄ )₄) was obtained as single crystals. The crystal structure was determined by X‐ray crystallography to reveal presence of one anion inside a cationic rectangular metallacycle { 2 ⊂ BF₄ }³⁺. Both structural evidence and DFT ‐calculated results indicate that the F atoms of the anion exert weak electrostatic attraction with hydrogen atoms of the bound bpa as the framework of the cationic metallacycle. The attractive interactions apparently play an important role in stabilizing some dynamically self‐assembled precursors so as to form the final anion‐included metallacycle. Without the electrostatic help from the anion, the self‐assembly of the empty metallacycle may be hindered by a rather large endothermic free energy. The favorable electrostatic stabilization is present not only for a anion but also for other anions such as , , and even when the flexible bpa is replaced by rigid 4,4′‐bipyridine (bpy). Based on the DFT results, the metallacycle 2 (BF₄ )₄ can be easily prepared in a one‐pot reaction of [Cu(MeCN )₄](BF₄ ) with three ligands.     

(Perhalogenmethylthio)heterocyclen. X. Säurekatalysierte Substitutionen an (Perchlorfluormethylthio)pyrrolen und deren agrobiologische Wirkung

(Perhalomethylthio)heterocycles. X

1 IX. Mitt.: s. [1].

. Acid-catalyzed substitutions on (perchlorofluoromethylthio)pyrroles and their agro-biological activities In the presence of C₄F₉SO₃H the (perhalomethylthio)pyrroles 1a–c react with Cl_3?nF_nCSCl (n = 1–3) to give mixtures of the 2,5- and 2,4-disubstituted pyrroles 2a–f and 3a–h . 2a and 3a react with CF₃SCl (catalyst CF₃SO₃H) yielding 2,3,5-tris (trifloromethylthio)pyrrole ( 4a ), which under similar conditions reacts further to give 2,3,4,5-tetrakis (trifluoromethylthio)pyrrole ( 5 ). As a by-product during the conversion of 3a to 4a 2,3,4-tris (trifluoromethylthio)pyrrole ( 4b ) is formed. The pyrroles 2a , 4a and 5 form the mercury salts 6a–c ; compound 5 yields also a silver salt 7 . The ¹H- and ¹⁹F-NMR. spectra are discussed and the agro-biological properties of the compounds investigated.     

Five- and six-membered platinacycles derived from phenantryl and anthracenyl imines

The reaction of [Pt₂Me₄(μ-SMe₂)₂] with ligands Me₂NCH₂CH₂NCHAr (2a, Ar=9-phenantryl; 2b, Ar=9-anthracenyl) carried out in acetone at room temperature produced the corresponding compounds [PtMe₂{9-(Me₂NCH₂CH₂NCH)C₁₄H₉}] (3) in which the imines act as bidentate [N,N^′] ligands. Refluxing toluene solutions of compounds 3 gave cyclometallated [C,N,N^′] compounds [PtMe{9-(Me₂NCH₂CH₂NCH)C₁₄H₈}] (4) as a mixture of two isomers containing either a five- or a six-membered metallacycles for 3a and as a single isomer containing a six-membered metallacycle for 3b. The reactions of compounds 4 with acetyl chloride and with methyl iodide produced, respectively, compounds [PtCl{9-(Me₂NCH₂CH₂NCH)C₁₄H₈}] (5) and [PtMe₂I{9-(Me₂NCH₂CH₂NCH)C₁₄H₈}] (6). All compounds were characterised by NMR spectroscopies and analytical data.     

Kinetics of fluorine atom reactions using resonance absorption spectrometry in the far vacuum ultraviolet reactions F + HCl,CH4, CHCl3 CHCl2F,and CHClF2

Atomic resonance absorption spectrometry with a nonreversed fluorine resonance lamp (～95 nm) has been used to study the kinetics of elementary reactions of ground state F²P_J atoms in a discharge-flow system. The following rate constants (in cm³/molec·sec)

1 All rate constants are given with 1.5 σ.

were determined at 298° K: The reaction F ₂P_J + HCl(1) was found to give J-excited Cl ₂P_1/2 atoms with a product branching ratio [Cl ₂P_1/2]/[Cl ₂P_3/2] = 0.10.     

Folded 2,5-diazapent-3-ene metallacycle in ene-diamido group 4 metal compounds: DFT and AIM analyses

Mononuclear complexes, which contain a dianionic ene-diamido ligand bound to a group 4 metal atom in the formal d⁰ configuration, are analyzed by the DFT method to interpret the electronic origin of the folding at the five-membered 2,5-diazapent-3-ene metallacycle moiety. Geometry optimizations were carried out for the following models, TiCl₂[o-(Me₃SiN)₂C₆H₄], Ti(OPh)₂(DAD), CpTiCl(DAD), CpTiMe(DAD) and Cp₂Zr(DAD) (DAD = HNCHCHNH). They show some common electronic features, the nature of the HOMO, in particular. In all cases, the latter results from the donation of a filled ene-diamido level into an empty σ metal orbital, this being maximized upon the folding of the metallacycle. Such a geometric rearrangement involves the filled nitrogen p_π lobes, while the CC π bond remains essentially uninvolved. The feature is confirmed by the application of the atom in molecules (AIM) theory, that provides no evidence of critical points between the metal center and the pair of two carbon atoms.     

Quantum chemical studies of propene,ethylene, acetylene and dihydrogen reactivity in the insertion reaction into the titanium-alkyl bond

Using the ab initio method of SCF MO LCAO

1 SCF MO LCAO: Self-consistent field molecular orbital linear combination of atomic orbitals.

in a valency-splitted basis of the Gaussian functions we have studied the addition of various monomers (C₃H₈, C₂H₄, C₂H₂) and dihydrogen to the titanium-alkyl bond in the complex H₂TiCH₃. The structure of transition states in the insertion reaction, heats of π-complex formation and activation energies for the insertion of the coordinated monomers have been calculated. The calculation results show that the reactivity decreases in the order C₂H₂ > C₂H₄ > C₃H₈ > H₂. According to the results obtained, the energy of the π^*-antibonding orbital of monomers can serve as an index of relative reactivity in the insertion reaction into the metal-alkyl bond.     

Stereochemistry of the Platinum Catalyzed Hydroformylation of Olefins

The deuterioformylation of (Z)- or (E)-2-butene catalyzed by [DIOP]Pt(SnCl₃)-Cl

1 DIOP=2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane.

gives predominantly erythro- or threo-1,3-[²H]₂-2-methylbutanal respectively. Hence, hydroformylation by this catalytic system must take place with cis-stereochemistry.     

Chemie von α-Aminonitrilen. 12. Mitteilung. Sondierungen über thermische Umwandlungen von α-Aminonitrilen

Chemistry of α-Amino Nitriles

1 11. Mitteilung: [1].

. Exploratory Experiments on Thermal Reactions of α-Amino Nitriles The paper extends a previously published report [4] on chemical properties of α-amino nitriles and of members of the C₃H₄N₂ ensemble (Scheme 1) as observed in experiments carried out under non-aqueous conditions. The reactions investigated and the observations made are summarized in some detail in the English footnotes (*) referring to Schemes 1–17 and Fig. 1.     

Preparation of ultrafine metal particles in processes of pulse mechanical action

Ultrafine metal particles (UFMP) (iron and cobalt) have been obtained in solid-state redox reactions of cyclopentadienyl--(3)-1,2-dicarbollyliron or cyclopentadienyl--(3)-1,2-dicarbollylcobalt with elemental sulfur ((C₅H₅)Fe³⁺(C₂B₉H₁₁)-S, (C₅H₅)Co⁵⁺C₂B₉H₁₁-S). These reactions are realized by the action of elastic wave (EW) pulses on powder compositions of these substances. Study of the UFMP obtained by the ferromagnetic resonance (FMR) method has shown that the sizes ofn · Co⁰ UFP lie in the range from 1 to 13 nm. UFP of cobalt and iron are also formed under the action of EW on samples containing (C₅H₅)Fe³⁺(C₂B₉H₁₁)-S or (C₅H₅)Co³⁺(C₂B₉H₁₁)-S within the film of tetrafluoroethylene and perfluoro-4-methyl-3,6-dioxaoct-7-ene-1-sulfonyl fluoride copolymer (CP). It is shown by the FMR method that FMR lines broaden on going from powder systems to systems containing CP films. It is supposed thatn · Co⁰ and n · Fe⁰ particles interact with polymeric matrices in the course of formation and stabilization of UFMP in the matrices.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2355–2358, December, 1995.This work was financially supported by the Russian Foundation for Basic Research (Project No. 94-03-09632).     

Kinetics and mechanism of the photolytic CO-substitutions of cyclopentadienyl(dicarbonyl)iron thiocarboxylate complexes,Cp′Fe(CO)2SCOR (Cp′ = C5H5, ButC5H4,1,3-Bu2tC5H3; R = alkyl,aryl)

The kinetics of the photolytic CO-substitution of CpFe(CO)₂SCOR [Cp = C₅H₅, Bu ^t C₅H₄, 1,3-Bu₂ ^t C₅H₃; R = Me, Bu ^t , Ph, 2-(O₂N)C₆H₄, 3-(O₂N)C₆H₄, 4-(O₂N)C₆H₄, 3,5-(O₂N)₂C₆H₃] with PPh₃ were studied in CH₂Cl₂ at 0 °C by i.r. spectroscopy. The reactions yielded exclusively the mono-CO-substituted derivatives, CpFe-(CO)(PPh₃) SCOR, and were found to follow second order kinetics with first order dependence on the concentration of each reactant. The differences in rates are discussed in terms of current knowledge pertaining to such reactions. An associative mechanism is proposed to account for the kinetic data of the reactions described.     

S-(N-(Thiocarbamoyl)benzimido)-dithiocarbamidsäureester

Zusammenfassung Die Synthese der Titelverbindungen3 (R ¹=R ²=C₂H₅;n-C₄H₉) durch Reaktionen von N-(N,N-Diethylthiocarbamoyl)-benzimidoylchlorid (2) mit Natriumdialkyldithiocarbamaten (1) in Aceton wird beschrieben. Die niedrigen Ausbeuten (bis 25% d.Th.) sind durch Nebenreaktionen bedingt. Die Strukturen der Verbindungen werden durch IR-,¹H-NMR-,¹³C-NMR-und Massenspektren bestätigt. Nebenreaktionen werden¹³C-NMR-spektroskopisch verfolgt und die Ergebnisse diskutiert.

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S-(N-(thiocarbamoyl)benzimido)dithiocarbamic esters

Summary The synthesis of the title compounds3 (R ¹=R ²=C₂H₅;n-C₄H₉) by reactions of N-(N,N-diethylthiocarbamoyl)benzimidechloride (2) with sodiumdialkyldithiocarbamates (1) in acetone is described. The low yields (<25%) are caused by the occurrence of side reactions. The structures of the compounds were confirmed by IR,¹H and¹³C NMR, and mass spectroscopy. Side reactions were detected by¹³C NMR spectroscopy; the results are discussed.

     

A tandem mass spectrometric investigation of (C2H5)2X+ ions (X = Cl,Br, I): The involvement of classical and nonclassical ethyl structures therein

The formation of diethyl halonium ions (C₂H₅)₂X⁺ (X = Cl, Br, I) by a variety of ion-molecule reactions is described. The dissociation characteristics (metastable and collision-induced dissociation mass spectra) of these ions and their isomers were studied in detail. Some of the neutral fragmentation products were examined by their collision-induced dissociative ionization mass spectra. The participation of classical (1, CH₃CH₂X⁺CH₂CH₃) and nonclassical forms of the ions was considered. Dissociation reactions for which loss of positional identity of H-D atoms took place, for example C₂H₄ loss (a common fragmentation of metastable ions) and C₂H₅ ⁺ formation, were interpreted as involving nonclassical ions, 2. It was concluded that the ion-molecule reactions produced both ion structures, but in different halogen-dependent proportions. For (C₂H₅)₂C1⁺ ions, 2 is the major species, for (C₂H₅)₂Br⁺ both 1- and 2-type ions are generated, whereas for (C₂H₅)₂I⁺ the classical form 1 must be the predominant structure.     

The He(Iα) Photoelectron Spectra of the Perfluoroderivatives of Trisannelated Benzenes and Tetrakisannelated Cyclooctatetraenes

The He(Iα) photoelectron (PE) spectra of tris(perfluorocyclobuta)benzene 4 (F)

1 3,3,4,4,7,7,8,8,11,11,12,12-Dodecafluorotetracyclo[8.2.0.0^2,5.0^6,9]dodeca-1,5,9-triene

, tris(perfluorocyclopenta)benzene 5 (F)

2 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-Octadecafluoro-2,3,4,5,6,7,8,9-octahydro-1H-trindene.

, tetrakis(perfluorocyclobuta)cyclooctatetraene 6 (F)

3 3,3,4,4,7,7,8,8,11,1l,l2,l2,l5,15,16,16-Hexadecafluoropentacyclo[12.2.0.0^2,5.0^6,9.0^10,13]hexadeca-1,5,9,13-tetraene.

, and of tetrakis(perfluorocyclopenta)cyclooctatetraene 7 (F)

4 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12-Tetracosafluoro-1,2,3,4,5,6,7,8,9,10,11,12-dodeca-hydrotetracyclopenta[a,c,e,g]cyclooctene.

are reported. A tentative assignment of the PE spectra is derived by empirical correlation with those of relevant reference compounds. The results suggest that 6 (F) retains the D_4h-conformation in the gas phase, i.e. A conformation with a planar cyclooctatetraene ring, as observed in the crystal. All four compounds exhibit a sharp increase of their first ionization energies, relative to the corresponding parent hydrocarbons, due to the perfluoro effect.     

m-Ferrocenylbenzoate-bridged lanthanide coordination polymers: Syntheses, structures, electrochemical and magnetic properties

A series of m-ferrocenylbenzoate [m-ferrocenylbenzoate = m-NaOOCH₄C₆Fc, Fc = (η⁵-C₅H₅)Fe(η⁵-C₅H₄)] lanthanide coordination polymers, namely [Ln(μ₂-OOCH₄C₆Fc)(η²-OOCH₄C₆Fc)(μ₂-η²-OOCH₄C₆Fc)(CH₃OH)₂]_n [Ln = La (1), Pr (2), Nd (3), Sm (4) and Gd (5)], have been synthesized by reactions of m-ferrocenylbenzoate with Ln(NO₃)₃·nH₂O. X-ray crystallographic analyses reveal that 1, 2 and 5 are essentially isostructural with unique one-dimensional linear chain structure. Three types of coordination modes for m-ferrocenylbenzoate are observed in the unit structure which consists of the eight-membered metallacycle Ln₂(COO)₂ and the rhomboid Ln₂O₂. Electrochemical studies indicate that 1-5 exhibit a reversible redox wave of Fe^II/Fe^III and the half-wave potentials of 1-5 are slightly more positive than that of m-ferrocenylbenzoic acid. Magnetic investigations show that an antiferromagnetic interaction between Gd(III) ions exists in 5.     

2–Butoxyethanol and benzyl alcohol reactions with the nitrate radical: Rate coefficients and gas‐phase products

The bimolecular rate coefficients k and k were measured using the relative rate technique at (297 ± 3) K and 1 atmosphere total pressure. Values of (2.7 ± 0.7) and (4.0 ± 1.0) × 10^?15 cm³ molecule^?1 s^?1 were observed for k and k, respectively. In addition, the products of 2‐butoxyethanol + NO₃^? and benzyl alcohol + NO₃^? gas‐phase reactions were investigated. Derivatizing agents O‐(2,3,4,5,6‐pentafluorobenzyl)hydroxylamine and N, O‐bis (trimethylsilyl)trifluoroacetamide and gas chromatography mass spectrometry (GC/MS) were used to identify the reaction products. For 2‐butoxyethanol + NO₃^? reaction: hydroxyacetaldehyde, 3‐hydroxypropanal, 4‐hydroxybutanal, butoxyacetaldehyde, and 4‐(2‐oxoethoxy)butan‐2‐yl nitrate were the derivatized products observed. For the benzyl alcohol + NO₃^? reaction: benzaldehyde ((C₆H₅)C(?O)H) was the only derivatized product observed. Negative chemical ionization was used to identify the following nitrate products: [(2‐butoxyethoxy)(oxido)amino]oxidanide and benzyl nitrate, for 2‐butoxyethanol + NO₃^? and benzyl alcohol + NO₃^?, respectively. The elucidation of these products was facilitated by mass spectrometry of the derivatized reaction products coupled with a plausible 2‐butoxyethanol or benzyl alcohol + NO₃^? reaction mechanisms based on previously published volatile organic compound + NO₃^? gas‐phase mechanisms. © 2012 Wiley Periodicals, Inc.

1 This article is a U.S. Government work and, as such, is in the public domain of the United States of America.

© 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 778–788, 2012     

Chloromethylsilane functionalised dendrimers: synthesis and reactivity

Tetraallylsilane was functionalised using (chloromethyl)dimethylsilane to give the first generation chloromethyl terminated dendrimer 1. The resulting dendrimer was successfully reacted with K[CpM(CO)₂] (Cp=η⁵-C₅H₅; M=Fe, Ru) to give Si[(CH₂)₃SiMe₂CH₂MCp(CO)₂]₄ functionalised dendrimers in satisfactory yield. Reaction of dendrimer 1 with NaI in acetone gave the -SiMe₂CH₂I functionalised dendrimer, while reactions of 1 with K[CpM(CO)₃] (M=Mo, W, Re), Li[C₅Me₄H], Na[C₅Me₄H], the cobaloxime nucleophile or tert-BuLi were not successful.     

Molecular, Thermodynamic, and Kinetic Parameters of the Free Radical C2H5 · in the Gas Phase

The wave function, energy, equilibrium geometry, and normal vibration frequencies of the ground state of the free radical C₂H₅ ^· were obtained by ab initio calculations with inclusion of electron correlation effects at the UB3LYP/6-311++G^{* *} level. The resulting molecular parameters were used to estimate the thermodynamic functions of an ideal gas of C₂H₅ ^·. From the thermodynamic functions of C₂H₅ ^·, I^·, C₂H₅I, C₂H₄, and HI and the kinetic curves of isothermal pyrolysis of ethyl iodide, the absolute rate constants of elementary reactions of free ethyl radical and the mentioned iodine compounds were estimated. The dissociation energy E _{D , 0}(C₂H₅-I) and the standard formation enthalpy _f H ⁰298 (C₂H₅ ^·) were found.