Showing papers in "Synthesis and Reactivity in Inorganic and Metal-organic Chemistry in 1977"
TL;DR: Tertiary phosphines of the type (C2Hj5O)3Si(CH2)3-P(C6H5)R /R = phenyl (Ia) and menthyl(Ib)/ were prepared by phosphination of the title compound with LiP(c6H 5)R.
Abstract: Tertiary phosphines of the type (C2Hj5O)3Si(CH2)3-P(C6H5)R /R = phenyl (Ia) and menthyl (Ib)/ were prepared by phosphination of the title compound with LiP(C6H5)R.
29 citations
TL;DR: In this paper, the influence of the trimethylsilyl group, incorporated in the borates I and II, on the stereoselectivity of the reaction was studied with the aid of 1H and 11B nmr.
Abstract: Sodium triethyl- (I) and triphenyl-trimethylsilylethynylborate (II), when treated with electrophilic reagents give (Z/E)-mixtures of tetrasubstituted alkenes III and IV. The influence of the trimethylsilyl group, incorporated in the borates I and II, on the stereoselectivity of the reaction was studied with the aid of 1H and 11B nmr. A novel rearrangement of bis-trimethylsilylalkenes IIId and IVd was also investigated.
24 citations
TL;DR: In this article, the generation of (n5-C5H5)Fe(CO)2 anion from commercially available sodium dispersion is reported, which is significantly better than other methods used in the 1iterature.
Abstract: The generation of [(n5-C5H5)Fe(CO)2] anion from [(n5-C5H5)Fe(CO)2] using commercially available sodium dispersion is reported. This procedure is significantly better than other methods used in the 1iterature. The usefulness of the procedure is demonstrated by the preparation of (n5-C5H5)Fe(CO)2(SnPh3), (n5-C5H5)Fe(CO)2Me, and (n5-C5H5)Fe(CO)(PPh3)(C(O)Me).
24 citations
TL;DR: Novel organometallic palladium (IV) complexes of the general formula [C13(C6F5) Pd (L-L)] have been prepared by the oxidative addition of chlorine to the corresponding palladium(II) compounds as discussed by the authors.
Abstract: Novel organometallic palladium(IV) complexes of the general formula [C13(C6F5) Pd (L-L)] have been prepared by the oxidative addition of chlorine to the corresponding palladium(II) compounds [Cl (C6F5)Pd(L-L)], (L-L) being 2,2′-bipyridine, 1,10-phenantroline or N,N,N″:N′-tetramethylethylenediamine
24 citations
TL;DR: The N, N'-ethylenebis (salicylideneiminato) cobalt (I) anion and similar nucleophilic anionic complexes have been shown to catalyze the dimerization or oligomerization of activated olefins as mentioned in this paper.
Abstract: The N, N'-ethylenebis (salicylideneiminato) cobalt (I) anion and similar nucleophilic anionic complexes have been shown to catalyze the dimerization or oligomerization of activated olefins.
14 citations
TL;DR: In this article, a highly reactive form of magnesium, intercalated in graphite, was prepared by reducing magnesium halides with C8K in ether or benzene, and Grignard reagents can be prepared from the graphite-trapped activated magnesium in practically quantitative yields in a fast reaction, even at low temperature and in non-ether solvents.
Abstract: A highly reactive form of magnesium, intercalated in graphite, was prepared by reducing magnesium halides with C8K in ether or benzene. Grignard reagents can be prepared from the graphite-trapped activated magnesium in practically quantitative yields in a fast reaction, even at low temperature and in non-ether solvents.
13 citations
TL;DR: In this article, the five-membered ring structure of the title compounds is confirmed by their molecular weight and 31P-nmr-spectra, and polymeric and metal-halogen exchange products are obtained in the case of RECl2 and transition element halides, respectively.
Abstract: Organoelement halides of the general formula R2'ECl2 (E = C, Si, Ge, Sn; R′ = H, Me, Et, n-Bu) and other compounds such as SCl2, (C5H5)2 TiCl2 and ZnCl2 react with alkali-phosphides RMP- (RP)n -PMR (n = 1,2; R = Ph, Cy; M = Na, K) forming the corresponding 1,2,3,4-tetraorgeno-cyclo-element-1,2,3,4-tetraphosphines. Polymeric and metalhalogen exchange products are obtained in the case of RECl2 (E = Al, N, As, Sb) and transition element halides, respectively. The five-membered ring structure of the title compounds is confirmed by their molecular weight and 31P-nmr-spectra.
13 citations
TL;DR: In this paper, the Raman and infrared spectra of methanetellurol (CH3TeH) are reported and compared with those of structurally related compounds.
Abstract: The Raman spectrum of methanetellurol (CH3TeH) is known, but the infrared spectrum has not yet been reported. In this paper the Raman and infrared spectra of CH3TeH are reported and compared with those of structurally related compounds: CH3Br, CH3OH, CH3SH and CH3SeH. Also, this report includes a description of the synthetic method and the chemical properties of CH3TeH.
12 citations
TL;DR: In this article, the synthesis of B(OEt)(SB) and B(SB)(SBH) types of derivatives (where SB− and SBH− are the anions of the Schiff bases, SBH2) is reported.
Abstract: Synthesis of B(OEt)(SB) and B(SB)(SBH) types of derivatives (where SB− and SBH− are the anions of the Schiff bases, SBH2) is reported. These are formed by 1:1 and 1:2 molar reactions of boron ethoxide with the bifunctional tridentate Schiff bases such as 3-(2-hydroxyethyl)amino-1-phenyl-2-buten-1-one, 3-(2-hydroxy-n-propyl)amino-1-phenyl-2-buten-1-one and 3-(2-hydroxyphenyl)amino-1-phenyl-2-buten-1-one respectively. The labile nature of the ethoxy groups in 1:1 derivatives has been shown by carrying out exchange reactions with an excess of t-butyl alcohol. The resulting derivatives have been characterized by elemental analysis, molecular weight determinations, conductance measurements and infrared and proton magnetic resonance spectra.
12 citations
TL;DR: In this paper, the insertion reactions of zirconium aminoalkoxides have been studied for the first time and have been shown to yield interesting derivatives with Zr-N bonds.
Abstract: N-Methylaminoalkoxides of zirconium of the type, Zr(OPri)4-n(O.CHR′.CH2.NR″R′)n, where R′ = R′ = H, R′ = Me; R′ = H, R′ = R′ = Me; R′ = R′ = R′ = Me; and n = 1–4, have been synthesized by the reactions of zirconium isopropoxide with aminoalcohols. These are characterized by elemental analyses and IR spectra. Insertion reactions of zirconium aminoalkoxides have been studied for the first time and have been shown to yield interesting derivatives with Zr-N bonds.
11 citations
TL;DR: In this paper, the coordination of 2-hydroxy-1-naphthalideneanilines containing different substituents in the aniline fragment was studied and the newly synthesized adducts of 1:2 stoichiometry [organotin(IV) chloride: Schiff base] were characterized by elemental analysis, thermogravimetric and infrared spectral data.
Abstract: Coordinative interactions of Ph2SnCl2, Me2SnCl2 and PhSnCl3 with 2-hydroxy-1-naphthalideneanilines containing different substituents in the aniline fragment have been studied. The newly synthesized adducts of 1:2 stoichiometry [organotin(IV) chloride: Schiff base] have been characterized by elemental analysis, thermogravimetric and infrared spectral data. Conductance measurements and electronic spectra indicate considerable dissociation of the compounds in solution.
TL;DR: In this article, the germanium-phosphorus bonds of ξ maphospholanes are very sensitive to protonic reagents which lead to ξ condary γ-germylated phosphines.
Abstract: 2-germaphospholanes are prepared in high yields by the reaction between RPLi2 and 1-diorganogermyl, 3-chloropropanes. Germylphosphines and germaphospholanes can be also prepared in good yields by cleavage of the germanium-oxygen bond of methoxygermanes by the P-H group of primary or secondary phosphines. The germanium-phosphorus bonds of ξ maphospholanes are very sensitive to protonic reagents which lead to ξ condary γ-germylated phosphines. The cleavage of germanium-phosphorus bonds is also observed with some electrophilic and nucleophilic reagents. Several functional γ-germylated phosphines have been isolated and characterized in this way.
TL;DR: In this article, 1:1 molar adducts of 2-aminomethylpyridine, 4-aminopyridine and 2-amino-4-methyl pyridine with BH3 were obtained by the reaction of the Lewis bases with trimethylamine-borane.
Abstract: 1:1 Molar adducts of 2-aminopyridine, 4-aminopyridine and 2-amino-4-methylpyridine with BH3 have been prepared by the reaction of the Lewis bases L with trimethylamine-borane. In all of the resulting products LBH3 the pyridyl nitrogen serves as donor site and no species of the type L(BH3)2 were observed. In contrast, 2-aminomethylpyridine reacts with BH3 only in a 1:2 molar ratio. The expected amine-bisborane was not isolated; rather, under the conditions employed, the species (2-dihydro-borylaminomethylpyridine)-borane, (2-H2B-NH-CH2-C5H4N)BH3, is obtained.
TL;DR: 2-Chloro-1, 3, 2-diox-arsolanes and -arsinanes can be synthesized in quantitative yields by reactions of the latter types of derivatives with arsenic trichloride.
Abstract: Reactions of arsenic trioxide with various 1,2-diols (viz., ethane-1, 2-diol; propane-1, 2-diol; butane-2, 3-diol and 2, 3-dimethylbutane-2, 3-diol), 1, 3-diols (viz., propane-1, 3-diol; butane-1, 3-diol and 2-methyl-pentane-2, 4-diol) and pentane-1, 5-diol in 1:2 and 1:3 molar ratios give the corresponding 2, 2′-oxybis (1, 3, 2-diox-arsolanes and -arsinanes) and 2,2′-alkylenedioxybis-(1, 3, 2-diox-arsolanes and -arsinanes) respectively as volatile liquids which are susceptible to hydrolysis. 2-Chloro-1, 3, 2-diox-arsolanes and -arsinanes can be synthesized in quantitative yields by reactions of the latter types of derivatives with arsenic trichloride.
TL;DR: In this paper, a free radical reaction between bis-ferrocenyl mercury and hexa-organo-di-stannanes was used to synthesize tri-Organo-stannylferrocenes.
Abstract: A synthesis of isomerically pure stannyl-ferrocenes is described which utilizes a free radical reaction between bis-ferrocenyl mercury and hexa-organo-di-stannanes. The yields of tri-organo-stannylferrocenes so obtained are generally superior to those obtained through the use of lithium derivatives of ferrocenes as intermediates. Further, the isomeric separation of mono-substituted compounds from the 1,1′-di-substituted compounds, which is always a prevalent complication in lithiation procedures, is eliminated.
TL;DR: In this paper, the synthesis of several model complexes for the metal complexes formed between aquatic or soil organic matter and metal ions was described, based on functional group analyses of the natural organic matter, and they chose ortho-substituted benzenes as chelating agents.
Abstract: This paper describes the syntheses of several model complexes for the metal complexes formed between aquatic or soil organic matter and metal ions. Based on functional group analyses of the natural organic matter, we chose ortho-substituted benzenes as chelating agents. They are salicylaldehyde, 2′-hydroxyaceto-phenone, methylsalicylate, and 2-methoxyphenol. A variety of cobalt(II), nickel(II), copper(II), iron(III), and chromium(III) complexes were prepared.
TL;DR: Three cinnamyl borates, B(OCH2-CH = CH-C6H5)3 (I), [B[OCH 2-CH=CH-C 6H5]2O (II) and [OB[O CH 2-Ch=CH C 6H 5]3 (III) have been synthesized by heating cinnamide alcohol with boric oxide under vacuo as discussed by the authors.
Abstract: Three cinnamyl borates, B(OCH2-CH = CH-C6H5)3 (I), [B(OCH2-CH=CH-C6H5)2]2O (II) and [OB(OCH2-CH=CH-C6H5)]3 (III) have been synthesized by heating cinnamyl alcohol with boric oxide under vacuo. (I) was also synthesized by alcoholysis of ethyl borate with cinnamyl alcohol. The reactions of aluminium isopropoxide with cinnamyl alcohol in different stoichiometric ratios yield A1[OCH(CH3)2]3-n (OCH2-CH=CH-C6H5)n (where n = 1,2 or 3). Tetracinnamoxides of titanium and germanium and pentacinnamoxides of niobium and tantalum as well as di-n-butyltin dicinnamoxide and tri-n-butyltin monocinnamoxide were also synthesized by alcoholysis reactions. IR and PMR spectral properties of these new derivatives have been discussed.
TL;DR: Two types of solid potassium peroxofluoro zirconate (IV) species have been synthesized for the first time in this paper, and they are K3.2. (O2)2.
Abstract: Two types of solid potassium peroxofluoro zirconate (IV) species have been synthesised for the first time. They are K3. Zr2. (O2)2. F7. (0.6–2) H2O and K2. Zr2. (O2)2. F6. (4–5) H2O. The first species is formed when the zirconium to fluoride mole ratios initially employed for the preparation are in the range 1:5 to 1:7, whereas the second one is formed when Zr (IV): F− employed for the preparation is 1:3.
TL;DR: In this article, a 1,2-addition of the pyridylamino and diphenylboryl moieties of the aminoborane across the CN double bond of the organic species was reported.
Abstract: (2-Pyridylamino)diphenylborane reacts with isocyanates and isothiocyanates in a 1,2-addition of the pyridylamino and diphenylboryl moieties of the aminoborane across the CN double bond of the organic species. Spectroscopic data suggest that the boron atom of the reaction products is in tetrahedral environment due to back-coordination with the pyridyl nitrogen.
TL;DR: Arylarsonates of dimethyltin (IV) of the general formula X-C6H4AsO3Sn(CH3)2 have been prepared.
Abstract: Arylarsonates of dimethyltin (IV) of the general formula X-C6H4AsO3Sn(CH3)2 (where X is H, p-CH3, p-OCH3, p-Cl, p-Br, o-NO2, o-NH2 and p-CH) have been prepared. These high melting and insoluble polymeric solids have been characterized by elemental analysis and infrared spectroscopy (4000–400 cm−1). A six coordinated structure has been suggested for all these compounds in which the arsonic acid group acts as a bridging group in polymeric structure.
TL;DR: The PtIMePh2(chel) type readily undergo substitution reactions with AgX (X=Cl, Rr, CN, SCN, NCO or N3) to give thermally and air-stable pseudohalo-complexes, which can easily be isolated as mentioned in this paper.
Abstract: The oxidative addition of RI (R=CH3, C2H3, C2H5, CH(CH(CH3)2 C6F5 or C6Cl5) to PtPh2(chel) (chel = 2,2′-bipyridine or 1, 10-phenantroline) only takes place for R=CH3. The resulting complexes of the PtIMePh2(chel) type readily undergo substitution reactions with AgX (X=Cl, Rr, CN, SCN, NCO or N3) to give thermally- and air-stable halo or pseudohalo-complexes, which can easily be isolated.
TL;DR: In this paper, the PH-bond was used to insert unsaturated systems such as aldehydes, ketones isothiocyanates, and electrophilic olefines into the PHbond.
Abstract: Hydrido-cyclotri(phosphazenes) insert unsaturated systems such as aldehydes, ketones isothiocyanates, and electrophilic olefines into the PH-bond. Their hydrogen may be replaced by halogen with CCl4 or CBrCl3, and by amino groups with CCl4/amine.
TL;DR: In this article, the nickel(II) tetrathiomolybdato complexes [NiL2MoS4] and [Ni3phen5(AsS4)2] have been prepared.
Abstract: The nickel(II) tetrathiomolybdato complexes [NiL2MoS4] (where L = ethylenediamine, ortho-phenanthroline and 2,2′-bipyridyl) and tetrathioarsenato complexes [Ni3en6(AsS4)2] and [Ni3phen5(AsS4)2] have been prepared. Their infrared and electronic spectra as well as magnetic moments suggest that Ni(II) has a distorted octahedral configuration and MS4 groups (M= MO, AS) are coordinated to nickel(II) rather than free anionic groups.
TL;DR: The reaction of silver ion with methoxide ion in methanol or with ethoxide ion with ethanol at 25°C affords highly unstable intermediates (presumably the silver alkoxides) which decompose rapidly to give metallic silver and unidentified oxidation products.
Abstract: The reaction of silver ion with methoxide ion in methanol or with ethoxide ion in ethanol at 25°C affords highly unstable intermediates (presumably the silver alkoxides) which decompose rapidly to give metallic silver and unidentified oxidation products. Silver salts of tert-butyl alcohol and phenol decompose somewhat more slowly, while phenols with electron-withdrawing groups afford stable silver salts.
TL;DR: In this article, the high yield syntheses of the trans-dimethyl complexes (CH3)2Co(BDM1,3pn) and (CD3) 2Co (BDM 1, 3pn) are reported.
Abstract: The high yield syntheses of the trans-dimethyl complexes (CH3)2Co(BDM1,3pn) and (CD3)2Co(BDM1,3pn) are reported. (BDM1, 3pn) is a mononegative, quadridentate, dioxime-diimime ligand formed by the condensation of 2,3-butanedionemonoxime and 1,3-propane-diamine in a 2/1 molar ratio.1) The compounds were characterized by infrared and proton magnetic resonance spectroscopy. Their reactivity to several weakly acidic solvents is discussed.
TL;DR: The new, aliphatic arsenic compounds [C8H17As(O)OH]2(CH2)n (n = 5−8, 10−12) have been prepared from octyldiethylaminochloroarsine in yields ranging from 38% to 75%.
Abstract: The new, aliphatic arsenic compounds [C8H17As(O)OH]2(CH2)n (n = 5−8, 10,12) have been prepared from octyldiethylaminochloroarsine in yields ranging from 38% to 75%.
TL;DR: In this paper, a synthetic approach for the preparation of the cis-bromofluorobis(ethylenediamine) and cis-chlorofluoric acid-chromi-um(II1) cations is described.
Abstract: A different synthetic approach for the preparation of the cis-bromofluorobis(ethylenediamine) and cis-chlorofluorobis(ethylenediamine)chromi-um(II1) cations is described. The complex cations were isolated as iodide salts and in the case of the chlorofluoro complex a perchlorate salt was also isolated.
TL;DR: In this article, the authors used the Yarovenko reagent to test the reactivity of the group X toward the reagent in terms of the Si-X bond.
Abstract: Organoslicon model compounds of the type R3SiX (where for R = CH3, X = Cl, OC2H5, OCOCH3, ONa, OC7H15, OC6 H5, OSi(CH3)3, NHSi(CH3)3, C6 H5, CH = CH2, CH2 OCH3, CH2 Cl and for R □ C2 H5, X □ H) were used to test the reactivity of the group X toward the Yarovenko reagent. Compounds containing Cl, H, OC2H5, OCOCH3, ONa, OC7H15, OC6H5, OSi(CH3)3, NHSi(CH3)3 groups undergo the cleavage of the Si-X bond to give R3SiF. By using heptanol, heptyloxytrimethylsilane, and hexamethyldisiloxane the temperature dependence of formations of trimethylfluorosilane, heptyl fluoride, and side products was determined in tetrahydrofuran and diethyl ether and this dependence was discussed in terms of the known mechanism of fluorination by the Yarovenko reagent.
TL;DR: In this article, the manganese ion was found to be in a pseudo octahedral environment, and its magnetic susceptibility, molar conductance, and visible spectral measurements suggest that the ion was formed by a pentadentate Schiff base ligand.
Abstract: Manganese(III) complexes incorporating pentadentate Schiff base ligands have been prepared from their manganese(II) precursors via two routes. These routes involve oxidation by molecular oxygen in the presence of an anion, and oxidation by iodine. Magnetic susceptibility, molar conductance, and visible spectral measurements suggest that the manganese ion is in a pseudo octahedral environment.
TL;DR: In this article, a general method for the synthesis of ferrocenyl-alkenes consists of acylation followed by lithium aluminum hydride reduction followed by in situ decomposition with 20% hydrochloric acid, overall yields range from 75-89%.
Abstract: This general method for the synthesis of ferrocenyl-alkenes consists of acylation followed by lithium aluminum hydride reduction followed by in situ decomposition with 20% hydrochloric acid, overall yields range from 75–89%.