Reactions of alkylcobalt complexes containing a tetradentate nitrogen-donating ligand

The reactions of RCo(BDM1,3pn)(H₂O) with light, heat, acids, electrophiles and nucleophiles were studied. (HBDM1,3pn is a mononegative, tetradentate dioxime-diimine ligand formed by condensing 2,3-butanedionemonoxime with 1,3-propanediamine in a 2/1 molar ratio; R = CH₃, C₂H₅, n-C₃H₇, n-C₄H₉, and C₆H₃CH_2-) Pyrolysis and photolysis of the alkyl complexes result in a cobalt(II) complex (anaerobic conditions) along with alkenes and alkanes. The major organic products from solid state pyrolysis at 200°C or photolysis in water are CH₄ (R = CH₃), C₂H₄ (R = C₂H₅), C₃H₆ (R = n-C₃H₇), C₄H₈ (R = n-C₄H₉) and (C₆H₅CH₂)₂ (R = C₆H₅CH₂). No alkyl—cobalt bond cleavage occurs with acids or bases in most cases. Two exceptions are the reactions with 3 M HNO₃ at 25°C and with 1 M NaOH at 52°C. Electrophiles like I₂ cleave the alkyl—cobalt bond forming RI and Co^III (BDM1,3pn)I₂. Nucleophilic reagents (N^-) displace the H₂O trans to the alkyl group to form RCo(BDM1,3pn)(N), but do not dealkylate the alkyl complex under the reaction conditions studied.     

Cyclic phosphites based on D-sorbitol and dulcitol

Conclusions Tricyclic triphosphites based on D-sorbitol and dulcitol with the general formula C₆H₈O₆(P-OR)₃, where R=C₂H₅-, n-C₃H₇-, and n-C₄H₉-in the case of sorbitol and R=C₂H₅ in the case of dulcitol, were synthesized for the first time.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1666–1668, July, 1970.     

Synthesis and properties of dicyclopentadienyltantalum hydride olefin compounds

Reactions of Cp₂TaCl₂ with RMgCl (R = n-C₃H₇, i-C₃H₇, n-C₄H₉, s-C₄H₉, n-C₅H₁₁ and C₅H₉) give tantalum hydride π-olefin complexes Cp₂Ta(H)L (L = C₃H₆, C₄H₈, C₅H₁₀ and C₅H₈). Two isomers of Cp₂Ta(H)C₃H₆ were obtained. The complexes are useful starting materials for the synthesis of other tantalum hydride species, e.g. Cp₂Ta(H)PEt₃ and Cp₂TaH₃.     

Use of organomagnesium compounds for the synthesis of organic derivatives of group II–V elements in a nonethereal medium

Summary For the primary alkyl halides (R=from C₂H₅ to n-C₉H₁₉; halogen=C1, Br, and I) and the simplest aryl halides (R=C₆H₅ and p-CH₃C₆H₄) it was shown that the organomagnesium synthesis in absence of catalysts for the Grignard reaction can be applied with success to the preparation of heteroorganic compounds of elements of Groups II–IV (mercury, boron, aluminum, silicon, germanium, tin, phosphorus, arsenic, antimony).     

共轭高分子的研究——Ⅶ.脂肪腈类的聚合

<正> 聚腈作为新的一类共轭高分子而引起注意。本文在前报的基础上进一步选择了一系列脂肪腈(乙腈、丙腈、戊腈、庚腈和苯乙腈),系统地研究它们在络合能力较强的付氏试剂(BF_3和TiCl_4等)作用下的聚合反应与机理,同时测定了各聚腈的物理性能。 1.腈的络合聚合 腈类与付氏试剂可形成定组成的络合物结晶:     

Studies on organophosphorus compounds XLVIII Synthesis of Dithioesters from P,S-Containing Reagents and Carboxylic Acids and Their Derivatives

2,4-Bismethylthio-1,3,2,4-dithiadiphosphetane 2,4- disulfide, IIa, is prepared from 0,0-dimethyldithiophosphoric acid, Ia, and P₄S₁₀ at 160°C. 2,4-Bis(4-phenoxyphenyl)-1,3,2,4- dithiadiphsophetane 2,4-disulfide, IIc, and 2,4-bis(4-phenylthiolophenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide, IId, are prepared at l60°C from P₄ S₁₀ and diphenylether and diphenylsulfides, respectively. Carboxylic acids RCOOH(R = CH₃ C₂H₅, n-C₃H₇, n-C₄H₉, C₆H₅CH₂, C₆H₈) react with compound Ia at 130°C to give the corresponding methyl dithioesters. Carboxylic acids RCOOH (R = C₆H₈-CH₂, C₆H₈) react with compound Ib at 200°C for 15 min to give the corresponding ethyl dithioesters, while low boiling acids (R = CH₃, C₂H₈, n-C₃H₇) yielded mixtures of the corresponding ethyl dithioester and ethyl carboxylate. Carboxylic acid chlorides RCOCl (R = ClCH₂, C₂H₅, t-C₄H₅ C₆H₅CH₂, C₆H₅, P-NO₂C₆H₄) react with compound IIa at 80°C to give the corresponding methyl dithioesters in good yields. S-Substituted thioesters react with IIC at 85°C to give the corresponding dithioesters in good yields. Dihydro2(3H)-furanone, VI, and 5-methyl-2(3H)-furanone, VII, react with IIa at 80°C; to dihydro-2(3H)-thiophenethione, VIII and 2,2'-dithiobis(5-methyl thiophene),IX, respectively. Also XI reacts with IIa,IIc, and IId to give VIII in nearly quantitative yields.     

Alcoholate Complexes of Nickel(II) Chloride

Alcoholate complexes of nickel chloride with the general formula, NiCL₂ · ROH (R = CH₃, C₂H₅, i-C₃H₇, n-C₄H₉, t-C₄H₉, t-C₅H₁₁, n-C₆H₁₃ and n-C₈H₁₇), synthesized either by the reaction of anhydrous nickel chloride with alcohols or by the replacement of methanol from NiCL₂ · MeOH with higher alcohols, depict interesting differences when R is a secondary or tertiary alkyl group instead of a primary group. A study of the magnetic susceptibility, thermogravimetric measurement, electron spin resonance and electronic reflectance spectra has been carried out to throw light on the structure of these derivatives.     

Spezielle Organoschwefel- und -selenverbindungen einiger Übergangsmetalle

Aluminum phenylselenolate and 1-naphthylselenolat react with TiCl₄, ZrCl₄, NbCl₅, TaCl₅, WCl₆ and CrCl₃ · 3THF giving compounds of types M(SeR)₄ (M = Ti, Zr, W; R = C₆H₅, C₁₀H₇) and M(SeR)₃ (M = Nb, Ta, Cr; R = C₆H₅, C₁₀H₇). By reaction of nickel(II), cobalt(II) and cobalt(III) acetylacetonates with thiophenol, selenophenol and 1-selenonaphthol polymeric compounds of composition Ni(XR)₂, Co(XR)_n (X = S, Se; R = C₆H₅, C₁₀H₇; n = 2 or 3) and Co(SC₆H₅)₂ · C₆H₅SH are obtained. [(n-C₄H₉)₃P]₂NiCl₂ and selenophenol in the presence of triethylamine give the monomeric compound [(n-C₄H₉)₃P]₂Ni(SeC₆H₅)₂.     

Systematische untersuchungen über das verhalten von organozinn-verbindungen gegenüber flüssigem schwefeldioxid : I. Reaktionen von tetraalkylstannanen mit flüssigem SO2

The SO₂ insertion into teraalkyltin compounds, R₄Sn (R = CH₃, C₂H₅, n-C₃H₇, i-C₃H₇, n-C₄H₉), was investigated depending on the presence of water, reaction temperature and reaction time. According to eqns. (1)–(5), the reaction products R₃SnO₂SR, R₂Sn(O₂SR)₂, (R₃Sn)₂SO₄, R₂SnSO₄ and R₂SnSO₃ were isolated. Especially; at low temperatures (<0°) the following order of decreasing reactivity of the teraorganostannanes toward SO₂ is established: R = C₂H₅ > CH₃ > n-C₃H₇ > n-C₄H₉ > i-C₃H₇     

Inorganic Chemistry Concepts,Vol. 6. Inorganic Stereochemistry : by D.L. Kepert,Springer-Verlag,Berlin; 227 pages,DM 154

The paramagnetic compounds [Os₂(OCOR)₄Cl₂] (R = n-C₃H₇, C₂H₇, C₂H₅, CH₂Cl) have been synthesized by reaction of [Os(OCOCH₃)₂Cl]_n with the appropriate acids and the binuclear tetracarboxylate bridged structure confirmed by X-ray analysis for R = n-C₃H₇, (OsOs distance 2.301 Å, cf. the related [Os₂(hp)₄Cl₂](CH₃CN)₂; OsOs, 2.357 Å) (hp = 2-hydroxypyridine anion).     

Novel reactions of phosphonium ylides with perhaloalkanes: First examples of halophilic attacks by phosphonium ylides and a facile route to α-haloalkylphosphonium salts

Phosphonium ylides Ph₃PCHR (R = H, CH₃, C₂H₅, n-C₃H₇, n-C₅H₁₁) react readily with perhalofluoroalkanes to afford regiospecifically α-haloalkylphosphonium salts Ph₃P⁺-CHXR Y⁻ (X = I, Br, Cl) in good yields. These reactions reveal a new type of reactivity of phosphonium ylides, i.e., the halophilic attack on CX bonds, and may be useful for the regiospecific synthesis of substituted haloolefins via Wittig reaction.     

Diorganotin(IV) complexes of N-protected dipeptides

Eight new diorganotin(IV) complexes of general formula R₂Sn(DP)₂ and [R₂Sn(DP)]₂O (DP = anion of N-benzoyl-dl-alanylglycine; R = CH₃, C₂H₅, n-C₄H₉, n-C₈H₁₇) have been prepared and characterised by IR, and ^119mSn Mössbauer spectroscopy. However, only two complexes, (DP)₂Sn(n-C₄H₉)₂ and (DP)₂Sn(n-C₈H₁₇)₂ were sufficiently soluble for NMR (¹H and ¹³C) studies. The 2 : 1 complexes are monomeric with distorted trans-octahedral structures. The 1 : 1 complexes are dinuclear with Sn-O-Sn bridges and trigonal bipyramidal geometry about tin. In both cases the dipeptide acts as an O,O-bidentate ligand.     

Analysis of sodium alkylsulphonates using filament heated in-beam electron impact mass spectrometry

Summary By means of the filament heated in-beam method at 280–450° C, the series of sodium alkylsulphonates (RSO₃Na, where R=C₂H₅ to n-C₁₂H₂₅) give very simple mass spectra: Na⁺, [RSO₃Na₂]⁺, which is the base peak except for R=n-C₄H₉, [(RSO₃)₂Na₃]⁺ and, in most cases, [(RSO₃)₃Na₄]⁺. Fragmentations other than these three or four peaks are observed only in the case of n-heptylsulphonate. The proposed method of analysis for simple alkylsulphonic acids is applicable to ordinary electron-impact mass spectrometers.

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Analyse von Natrium-alkylsulfonaten durch Elektronenstoß-Massenspektrometrie mit Probenerhitzung im Elektronenstrahl

Zusammenfassung Mit Hilfe dieser Methode (280–450° C) erhält man für Natriumalkylsulfonate (RSO₃Na mit R=C₂H₅ bis n-C₁₂H₂₅) sehr einfache Massenspektren: Na⁺, [RSO₃Na₂]⁺ (Basispeak mit Ausnahme von R=n-C₄H₉), [(RSO₃)₂Na₃]⁺ und in den meisten Fällen [(RSO₃)₃Na₄]⁺. Andere Fragmentierungen als diese 3 oder 4 Peaks wurden nur bei n-Heptylsulfonat beobachtet. Dieses Verfahren zur Analyse einfacher Alkylsulfonsäuren ist für übliche Elektronenstoß-Massenspektrometer verwendbar.

     

The effect of carboxylate anions on the formation of clathrate hydrates of tetrabutylammcnium carboxylates

The solid-liquid phase diagrams of binary mixtures of water with tetrabutylammonium carboxylate having an unsaturated alkyl group in the carboxylate anion ((n-C₄H₉)₄NOOCR; R=C₂H₃–C₉H₁₇) were examined in order to confirm the formation of clathrate-like hydrates. The results are summarized as follows: (1) the formation of a clathrate-like hydrate is newly confirmed for all the 13 carboxylates examined; (2) these hydrates are classified into three groups I, II, and III on the basis of the hydration numbers; (3) the group I hydrates, which are formed by the carboxylates with R=C₂ and R=C₃, have hydration numbers around 30 and are the most stable hydrates among those examined in this study; (4) the group II hydrates, with hydration numbers around 39, are formed by all the carboxylates with R=C₄ and C₅ including sorbate and are less stable than the group I hydrates; (5) the group III hydrates, with hydration numbers around 30 like the group I hydrates, are formed by carboxylates with long alkyl chains such as 2-octenoate and 2-decenoate and are generally unstable.     

Dealkylation of alkylcobalt complexes by the mercury(II) electrophile

The dealkylation of a variety of RCo(BDMBg)⁺ complexes by Hg²⁺ is discussed. (The ligand BDMBg^- is formed by the condensation of two moles of 2,3-butanedionemonoxime with one mole of 1,3-propanediamine or 1,2-ethanediamine.) The products of the dealkylation reaction are Co^III(BDMBg)(H₂O)²⁺₂ and RHg⁺. All reactions are first order in the [Hg²⁺]. The second order rate constants (k₂) vary from 5.9 M^-1 sec^-1 (R = CH₃) to 5.7 x 10^-3M^-1 sec^-1 (R = n-C₃H₇). The relative rates for R are: CH₃ ? C₂H₅ τ C₆H₅CH₂ τ n-C₄H₉ ? n-C₃H₇. This order and other evidence are indicative of an S_E2 mechanism with an attack by Hg²⁺ on the carbon bonded to the cobalt.     

Darstellung und Eigenschaften von Diorganyl-bis(seleninato-O,O′)-Komplexen des Bleis und Zinns

Preparation and Properties of Diorganyl-bis(seleninato-O,O′) Complexes of Lead and Tin The colourless, thermically stable diorganyl-bis(seleninato-O , O ′) complexes of lead and tin R₂E(O₂SeR′)₂[E = Pb (1) , Sn (2) ] are obtained by reaction of diorganyllead- and -tindichlorides R₂ECl₂ (R = C₆H₅, CH₃, C₂H₅, n-C₄H₉) with different sodiumseleninates R′SeO₂Na (R′ = C₆H₅, CH₃, C₂H₅) at 20°C. On the basis of their i.r., Raman, and Mößbauer spectra and their slightly solubility in all organic solvents a polymeric structure is supposed in which each two R′SeO₂ - ligands are linking two lead and tin atoms respectively (c.n. = 6) intermolecular (seleninato-O , O ′). The organic residues are in trans-position.     

Reaction of alkoxyl organomercury compounds with chloroform

Conclusions Derivatives of trichloromethylmercury RHgCCl₃ (R=n-C₃H₇, cyclo-C₆H₁₁, C₆H₅CH₂, and C₆H₅), which are stable in the absence of air, were obtained in almost quantitative yield by the reaction of the corresponding mercury tert-butoxides RHgOC(CH₃)₃ with chloroform at room temperature.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2803–2805, December, 1968.     

Structure of salts of substituted 2-alkylthiotetrahydropyrimidines

The structure and ring-chain tautomerism of 2-alkylthio-3,4,6,6-tetramethyl-4-hydroxy-3,4,5,6-tetrahydropyrimidine hydrohalides (Alk = CH₃, C₂H₅, n-C₃H₇, n-C₄H₉, iso-C₄H₉, CH₂C₆H₅ Hal = Cl, Br, I) were analyzed by means of UV, IR, and PMR spectroscopy. It is shown that the cations of the salts in the crystalline state and in solutions exist primarily in the cyclic form.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 695–698, May, 1982.     

Fluoraustauschreaktionen an Metalltrifluorphosphin-Komplexen. IX. Zum Reaktionsverhalten von Tetrakis(trifluorphosphin)nickel(0) gegenüber Alkyl(trimethylsilyl)aminen und -amiden

Fluorine Exchange in Trifluorophosphine Metal Complexes. IX¹. (Reactions of Tetrakis(trifluorophosphine)nickel(0) with Alkyl(trimethylsilyl)amines and Amides²) Alkylaminodifluorophosphine complexes Ni(PF₃)_4-n(PF₂NHR)_n (n = 1, 2, 3) 8–11 and Me₃SiF are obtained, if alkyl(trimethylsilyl)amines NHR(SiMe₃) (R?CH₃ and n-C₄H₉) are reacted with Ni(PF₃)₄ ( 1 ). The mechanism of these peripheric reactions is discussed by assuming a four centered type intermediate. However reactions of 1 with the lithium amides LiNR(SiMe₃) (R = CH₃, C₂H₅, n-C₄H₉, and C₆H₅) yield LiF and the difluorotrimethylsilylaminophosphine complexes Ni(PF₃)_4-n[PF₂NR(SiMe₃)]_n (n = 1, 3, 4) 12–18 .     

Synthese,Charakterisierung und Kristallstrukturen von Tetraiodoferraten(III)

Preparation, Characterization, and Crystal Structures of Tetraiodoferrates(III) The extremely air and moisture sensitive tetraiodoferrates MFeI₄ with M = K, Rb and Cs have been synthesized by reaction of Fe, MI and I₂ at 300°C in closed quartz ampoules. The essentially more stable alkylammonium tetraiodoferrates NR₄FeI₄ with R = H, C₂H₅, n-C₃H₇, n-C₄H₉ and n-C₅H₁₁ can be obtained by reaction of Fe, NR₄I and I₂ in nitromethane. The Raman and UV/Vis-spectra of the black compounds show the existence of tetrahedral [FeI₄]^? ions in the structures. The crystal structure of the monoclinic CsFeI₄ (CsTlI₄ type, spgr P2₁/c; a = 7.281(1) Å; b = 17.960(3) Å; c = 8.248(2) Å; β = 107.35(15)°) is built up by tetrahedral [FeI₄]^? ions and CsI₁₁ polyhedra. The crystal structure of the orthorhombic (n-C₅H₁₁)₄NFeI₄ (spgr Pnna; a = 20.143(4) Å; b = 12.683(3) Å; c = 12.577(3) Å) contains tetrahedral [(n-C₅H₁₁)₄N]⁺ ions and [FeI₄]^? ions, respectively.