Reaction of benzyl chloride with propylene and trifluoropropene under metallocomplex initiation conditions

The reactions of benzyl chloride with propylene and 3,3,3-trifluoropropene in the presence of Fe(CO)₅ ` + DMF were studied. With propylene, the reaction stops at the addition stage with the simultaneous formation of dibenzyl. In the case of 3,3,3-trifluoropropene, a telomerization takes place, whereby the second growing radical C₆H₅CH₂CH₂CH(CF₃)CH₂HCF₃ practically completely isomerizes with a 1,5-migration into the radical C₆H₅HCH₂CH(CF₃)CH₂CH₂CF₃. To confirm the structure of the isolated compounds, chromato-mass-spectrometry and¹³C NMR were used.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1384–1388, June, 1991.     

Radical-type addition of benzyl bromide to vinyl chloride: the kinetics and activation energy of the process

Radical telomerization of vinyl chloride with benzyl bromide and the competitive reaction of benzyl bromide with vinyl chloride and trimethylvinylsilane have been studied. The relative rate constant for the addition of C₆H₅C · H₂ to vinyl chloride,k _rel (with respect to trimethylvinylsilane), is close to unity, whereas the activation energy of the addition of C₆H₅C^.H₂ to vinyl chloride is considerably lower (by 7 kcal mol^–1) than in the reaction involving trimethylvinylsilane. The possible fragmentation of the radical-adduct C₆H₅CH₂CH₂C^.HCl was suggested as one of the possible reasons of underestimation ofk _rel. The activation energy was estimated by the MPDO/3 method.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 886–888, May, 1993.     

Reaction of gem-trichloroalkanes with unsaturated compounds in presence of Fe(CO)5 and a cocatalyst

Conclusions The following reactions were effected in the presence of the coordination initiators Fe(CO)₅ + i-C₃H₇OH (or Hexametapol): a) Telomerization of vinyl chloride with 1,1,1-trichloropropane and 1,1,1,3,3-pentachloropropane. Telomers that contain 1–3 monomeric units in the molecule were isolated, b) The addition of 1,1,1,3-tetrachloropropane and 1,1,1-trichloroethane to isobutylene; the adducts were obtained in good yields, c) The reaction of allyl chloride with 1,1,1,3-tetrachloropropane, which leads to the formation of the adduct and by-products as the result of the partial fragmentation of the ClCH₂CH₂CCl₂CH₂CHCH₂Cl radicals with the cleavage of chlorine atom.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 174–177, January, 1977.     

Reaction of 1,1,1-trichloroethane or carbon tetrachloride with allyl chloride,initiated by the Fe(CO)5-isopropanol system

Conclusions The reaction of CCl₃CH₃ and CCl₄ with allyl chloride in the presence of Fe(CO)₅ and isopropanol yields a mixture of products, the main component of which is the adduct RCCl₂CH₂CHClCH₂Cl (R=Cl, CH₃). The RCCl₂CH₂CH= CH₂ were also isolated, which represent the fragmentation product of the intermediately formed radical and its adduct with the telogen, namely RCCl₂CH₂CHClCH₂CCl₂R.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2004–2008, September, 1973.     

Homolytic addition of benzyl bromide to unsaturated compounds in conditions of metal-complex initiation

Radical addition of benzyl bromide to unsaturated compounds containing substituents of a different polar nature, CH₂=CHX (X=C₄H₉, SiMe₃, CF₃, CO₂Me, CN, H), was conducted in the presence of the Fe(CO)₅ + DMF (HMPA) system. Adducts were obtained and their structure was demonstrated by¹³C NMR and mass spectrometry.A. N. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 2347–2352, October, 1992.     

Kinetics and products of the gas-phase reactions of the OH radical and O3 with allyl chloride and benzyl chloride at room temperature

The kinetics of the gas-phase reactions of allyl chloride and benzyl chloride with the OH radical and O₃ were investigated at 298 ± 2 K and atmospheric pressure. Direct measurements of the rate constants for reactions with ozone yielded values of ??(O₃ + allyl chloride) = (1.60 ± 0.18) × 10^?18 cm³ molecule^?1 s^?1 and ??(O₃ + benzyl chloride) < 6 × 10^?20 cm³ molecule^?1 s^?1. With the use of a relative rate technique and ethane as a scavenger of chlorine atoms produced in the OH radical reactions, rate constants of ??(OH + allyl chloride) = (1.69 ± 0.07) × 10^?11 cm³ molecule^?1 s^?1 and ??(OH + benzyl chloride) = (2.80 ± 0.19) × 10^?12 cm³ molecule^?1 s^?1 were measured. A study of the OH radical reaction with allyl chloride by long pathlength FT-IR absorption spectroscopy indicated that the co-products ClCH₂CHO and HCHO account for ca. 44% of the reaction, and along with the other products HOCH₂CHO, (ClCH₂)₂CO, and CH₂ ? CHCHO account for 84 ± 16% of the allyl chloride reacting. The data indicate that in one atmosphere of air in the presence of NO the chloroalkoxy radical formed following OH radical addition to the terminal carbon atom of the double bond decomposes to yield HOCH₂CHO and the CH₂Cl radical, which becomes a significant source of the Cl atoms involved in secondary reactions. A product study of the OH radical reaction with benzyl chloride identified only benzaldehyde and peroxybenzoyl nitrate in low yields (ca. 8% and ?4%, respectively), with the remainder of the products being unidentified.     

Relative kinetics of the radical addition of benzyl bromide to unsaturated compounds

The relative rate constants of the addition of the C₆H₅CH₂ radical to unsaturated compounds CH₂=CHX (X = C₄H₉, SiMe₃, CF₃, CO₂Me, CN) were determined under the conditions of initiation by the Fe(CO)₅ + DMF system or by benzoyl peroxide. Depending on the values of the relative addition rate constants, the monomers can be arranged into the following series (X): CF₃C₄H₉32Me5 + DMF system, the addition stage proceeds by a free radical mechanism.A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 9, pp. 2017–2022, September, 1992.     

Spectroscopic study of vinylidene chloride—Vinyl chloride copolymers

Summary Deuteration technique was applied to study the micro structures of copolymer series VDC/VC by infrared spectroscopy and high resolution NMR. The CH₂ bending modes of chlorine atom containing polymers assigned as follows; –CCl₂CH₂CCl₂– 1405 cm^–1 (cryst.) and 1410 cm^–1 (amorph.), –CHClCH₂CCl₂– 1422 cm^–1, –CHClCH₂CHCl– 1428 cm^–1 (cryst.) and 1432 cm^–1 (amorph.) –CHClCH₂CH₂CHCl– 1445 cm^–1 and –CCl₂CH₂CH₂CCl₂– 1448 cm^–1. This infrared interpretation shows that only the head to tail addition occurs in the copolymerisation. Nine peaks of the methylene protons were observed clearly in the NMR spectra of the copolymers. The study of the deuterated copolymers revealed that the effects of the chemical groups until the third at both sides from the marked methylene and the stereo configuration of long VC part should be considered to assign the NMR spectra. The CCl₂ group made the chemical shift of the methylene proton to appear at lower magnetic field and the CHCl group gave the opposite behavior.

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Zusammenfassung Mit deuterierten Monomeren wurde die Mikrostruktur der Copolymerenserie Vinyliden-Chlorid/Vinyl-Chlorid im Infraroten und mit hochauflösender Kernresonanz untersucht. Für die Biegeschwingung der Chloratome enthaltenden Polymeren der Methylengruppe ergeben sich folgende Werte: –CCl₂CH₂CCl₂– 1405 cm^–1 (krist.) und 1410 cm^–1 (amorph.), –CHClCH₂CCl₂– 1422 cm^–1, –CHClCH₂CHCl– 1428 cm^–1 (krist.) und 1432 cm^–1 (amorph.), –CHClCH₂CH₂CHCl– 1445 cm^–1 und –CCl₂CH₂CH₂CCl₂– 1448 cm^–1.Diese Interpretation des Infraroten zeigt, daß nur die Kopf-Schwanz-Addition bei der Copolymerisation stattfindet. Neun Maxima des Methylenprotons wurden deutlich in den NMR-Spektren der Copolymeren beobachtet. Die Untersuchungen an den deuterierten Copolymeren zeigen, daß die Effekte der chemischen Gruppen bis zur dritten nach beiden Seiten vom markierten Methylen und die Stereokonfiguration von langen Vinyl-Chlorid-Anteilen betrachtet werden müssen, um die NMR-Spektren zu beschreiben. Die CCl₂-Gruppe läßt die chemische Verschiebung des Methylen-protons bei geringeren magnetischen Feldern und die CHCl-Gruppe bei höheren erscheinen.

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With 5 figures in 13 details and 4 tables     

Studies on interaction of isocyanide with transition metal complexes : XI. Photochemical reactions of isocyanide complexes of iron

The photochemical reaction of π-C₅H₅Fe(CO)(CNC₆H₁₁)COCH₃ (I) gave the heterocyclic compound π-C₅H₅Fe(CO)[(C=NC₆H₁₁)₂(CH₃)] (II) involving N-coordination to the iron atom. The analogous complex is obtained by the photo-induced reaction of π-C₅H₅Fe(CO)₂CH₃ with C₆H₁₁NC. A similar reaction of π-C₅H₅Fe(CO)[CNC(CH₃)₃]CH₃ with C₆H₁₁NC gave π-C₅H₅Fe(CO)[(C=NC₆H₁₁) {C=N(CH₃)₃}(CH₃)] (IV) involving different N-substituted imino groups. The possible pathways leading to formation of II are discussed. The mass spectra of these complexes were also investigated.     

Synthesis and some properties of coordination compounds based on p-toluenesulfonic acid

Conclusions Soluble coordination polymers of p-toluenesulfonic acid were obtained with the metal carbonyls Mn₂(CO)₁₀ and Fe(CO)₅, and with Mn(CH₃COO)₂.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 440–442, February, 1968.     

Telomerization of ethylene with phenyldiazonium chloride

Conclusions A study was made of the reaction of ethylene with phenyldiazonium chloride under the conditions of the Meerwein reaction. Telomers having the structure C₆H₅(CH₂CH₂)_nCl, where n=1 or 2, were identified, and also biphenyl, and the p- and o-chlorobiphenyls.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 179–180, January, 1971.     

Partial oxidation and oxidative condensation of methane with the participation of N2O on a V2O5/SiO2 catalyst

The catalytic reaction of CH₄, with N₂O at 773–823 K on a V₂O₅/SiO₂ catalyst affords products of the partial oxidation (HCHO and CH₃OH), exhaustive oxidation (CO), and oxidative condensation (C₂H₅OH and CH₃CHO) of methane. A mechanism is proposed for the complex reaction, including the intermediate compounds V⁵⁺O and V⁴⁺CH₃OH as common intermediates for all the routes.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 23, No. 5, pp. 641–646, September–October, 1987.     

Metal carbonyl catalysis of carbon monoxide and formate reactions

The water gas shift reaction (CO + H₂O = CO₂+ H₂) is catalyzed by aqueous metal carbonyl systems derived from simple mononuclear carbonyls such as Fe(CO)₅ and M(CO)₆ (M = Cr, Mo, and W) and bases in the 140–200 °C temperature range. The water gas shift reaction in a basic methanol-water solution containing Fe(CO)₅ is first order in [Fe(CO)₅], zero order in [CO], and essentially independent of base concentration and appears to involve an associative mechanism with a metallocarboxylate intermediate [(CO)₄Fe-CO₂H]^–. The water gas shift reactions using M(CO)₆ as catalyst precursors are first order in [M(CO)₆], inverse first order in [CO], and first order in [HCO₂ ^–] and appear to involve a dissociative mechanism with formatometallate intermediates [(CO)₅M-OCHO]^–.The Reppe hydroformylation of ethylene to produce propionaldehyde and 1-propanol in basic solutions containing Fe(CO)₅ occurs at 110–140 °C. This reaction is second order in [Fe(CO)₅], first order in [C₂H₄] up to a saturation pressure >1.5 MPa, and inhibited by [CO]. These experimental results suggest a mechanism where the rate-determining step involves a binuclear iron carbonyl intermediate. The substitution of Et₃N for NaOH as the base facilitates the reduction of propionaldehyde to 1-propanol but results in a slower rate for the overall reaction.The homogeneous photocatalytic decomposition of the formate ion to H₂ and CO₂ in the presence of Cr(CO)₆ appears to be closely related to the water gas shift reaction. The rate of H₂ production from the formate ion exhibits saturation kinetics in the formate ion and is inhibited by added pyridine. The infrared spectra of the catalyst solutions indicate an LCr(CO)₅ intermediate. Photolysis of the Cr(CO)₆/formate system in aqueous methanol in the presence of an aldehyde RCHO (R =n-heptyl,p-tolyl, andp-anisyl) results in catalytic hydrogenation of the aldehyde to the corresponding alcohol RCH₂OH by the formate ion. Detailed kinetic studies onp-tolualdehyde hydrogenation by this method indicates saturation kinetics in formate ion, autoinhibition by thep-tolualdehyde, and a threshold effect for Cr(CO)₆ at concentrations >0.004 mol L^–1. The presence of an aldehyde can interrupt the water gas shift catalytic cycle by interception of an HCr(CO)₅ ^– intermediate by the aldehyde.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1533–1539, September, 1994.     

Synthesis and Spectra of Cationic Bis(tertiary phosphine) derivatives of cycloheptatrienyliummolybdenum and cyclopentadienyliron complexes

Reaction of [(η-C₇H₇)Mo(CO)₃][PF₆] and [(η-C₅H₅)Fe(CO)₂CH₃CN][PF₆] with ditertiary phosphine ligands afforded products of three types; the monosubstituted complexes [(Ring)M(CO)₂Ph₂P(CH₂)_nPPh₂][PF₆] (Ring = η-C₇H₇, M = Mo, N = 1; Ring = η-C₅H₅, M = Fe, N = 1 and 2), the chelated complexes [(Ring)M(CO)Ph₂P(CH₂)_nPPh₂][PF₆] (Ring = η-C₇H₇, M = Mo, N = 1 and 2; Ring = η-C₅H₅, M = Fe, N = 1 and 2), and the dinuclear complex [{(η-C₇H₇)Mo(CO)₂}₂ -μ- Ph₂PCH₂CH₂PPh₂][(PF₆)₂]. Spectroscopic properties, including ³¹P NMR, are reported.     

Rhodium(I) carbonyl complexes of chalcogen functionalized tripodal phosphines, [CH3C(CH2P(X)Ph2)3] {X = O, S, Se} and their reactivity

The reaction of dimeric rhodium precursor [Rh(CO)₂Cl]₂ with two molar equivalent of 1,1,1-tris(diphenylphosphinomethyl)ethane trichalcogenide ligands, [CH₃C(CH₂P(X)Ph₂)₃](L), where X = O(a), S(b) and Se(c) affords the complexes of the type [Rh(CO)₂Cl(L)] (1a–1c). The complexes 1a–1c have been characterized by elemental analyses, mass spectrometry, IR and NMR (¹H, ³¹P and ¹³C) spectroscopy and the ligands a–c are structurally determined by single crystal X-ray diffraction. 1a–1c undergo oxidative addition (OA) reactions with different electrophiles such as CH₃I, C₂H₅I and C₆H₅CH₂Cl to give Rh(III) complexes of the types [Rh(CO)(COR)ClXL] {R = –CH₃ (2a–2c), –C₂H₅ (3a–3c); X = I and R = –CH₂C₆H₅ (4a–4c); X = Cl}. Kinetic data for the reaction of a–c with CH₃I indicate a first-order reaction. The catalytic activity of 1a–1c for the carbonylation of methanol to acetic acid and its ester is evaluated and a higher turn over number (TON = 1564–1723) is obtained compared to that of the well-known commercial species [Rh(CO)₂I₂]⁻ (TON = 1000) under the reaction conditions: temperature 130 ± 2 °C, pressure 30 ± 2 bar and time 1 h.     

The chemistry of the transition metalcarbon σ-bond. Insertion reactions between stannous chloride and h1-allyl and h1-propargyl complexes of h5-cyclopentadienyldicarbonyliron

The reactions between h⁵-CpFe(CO)₂R (R = CH₂CHCH₂; CH₂CMe=CH₂; CH₂CHCHMe; CH₂CHCMe₂) and stannous chloride in tetrahydrofuran afford the insertion products h⁵-CpFe(CO)₂SnCl₂R. When treated with stannous chloride in methanol or with excess stannous chloride in tetrahydrofuran, h⁵-CpFe(CO)₂CH₂CMeCH₂ affords primarily h⁵-CpFe(CO)₂SnCl₃. The allenyl, 2-butynyl or cationic isobutylene complexes (R = CHCCH₂; CH₂ CCMe; CH₂CMe⁺₂) yield only h⁵-CpFe(CO)₂SnCl₃. Stannous iodide reacts with h⁵-CpFe(CO)₂CH₂CHCH₂ in benzene to form h⁵-CpFe(CO)₂I. Plumbous chloride in methanol fails to react with the above complexes.     

The synthesis and characterization of metal-containing vinylic monomers of iron and tungsten

A series of metal-containing vinylic monomers of the type L_nM(COC₆H₄CH=CH₂) and L_nM (COCH=CHC₆H₅) [L_nM = (η⁵-C₅H₅)Fe(CO)₂, (η⁵-C₅Me₅)Fe(CO)₂ and (η⁵-C₅H₅)W(CO)₃] were prepared by the reaction of the appropriate metal anion with either 4-vinylbenzoyl chloride or cinnamoyl chloride. (η⁵-C₅H₅)(CO)₂FeCOCH=CH₂ was prepared by the reaction of Na[(η⁵-C₅H₅)Fe(CO)₂] and acryloyl chloride, whereas the compound (η⁵-C₅H₅)(CO)₂Fe(C₆H₄CH=CH₂) was prepared via a transmetallation reaction using a palladium catalyst. All compounds were fully characterized using FTIR, ¹H and ¹³C NMR spectroscopy and mass spectrometry. Copyright © 1998 John Wiley & Sons, Ltd.     

The reversible decarbonylation of methyl- and acetyldicarbonyl(η5-cyclopentadienyl)iron complexes in polyvinyl-chloride film matrices at 12–200 K

Infrared spectroscopic experiments using polyvinyl chloride film matrices at 12–200 K have shown for the first time that the photoinduced decarbonylation of Fe(η⁵-C₅H₅)(CO)₂(COCH₃) is thermally reversible, and that the photolysis of Fe(η⁵-C₅H₅)(CO)₂(CH₃) leads to the reversible formation of the new species Fe(η⁵-C₅H₅)(CO)(CH₃).     

Optisch aktive übergangsmetall-komplexe : VIII. (+)- und (−)-C5H5Fe(CO)[CN-CH(CH3)(C6H5]J

The interaction of C₅H₅Fe(CO)₂I with (+)-α-methylbenzyl isocyanide yields the diastereoisomeric pair (+)- and (−)-C₅H₅Fe(CO)[CN-CH(CH₃)- (C₆H₅)]I. The two diastereoisomers can be separated on the basis of their different solubilities by repeated precipitation from methylene chloride/pentane. Excluding light the complexes are configurationally stable in the solid state as well as in solution. In daylight, however, the optical rotations decrease rapidly (photoracemisation). The ORD and CD spectra (+)- and (−)-C₅H₅Fe(CO)[CN-CH(CH₃)(C₆H₅)]I show pronounced Cotton effects.     

Chlorine and hydrogen transfer by metal carbonyl intermediates

The reduction of 1,1,1,5-tetrachloropentane by toluene in the presence of the Fe(CO)₅ or M(CO)₆ (M=Cr, Mo, W) in conjunction with triphenylphosphine was investigated. It was shown that the chlorine-containing metal carbonyl intermediates formed in the process take part in the transfer of the chlorine atom to the benzyl radicals. It was shown that HMn(CO)₅ is not the main intermediate responsible for the transfer of hydrogen by the chloroalkyl radicals, which are formed during the reduction of 1,3,3,5-tetrachloropentane by triethylsilane in the presence of Mn₂(CO)₁₀.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 927–930, April, 1991.