G. Z. Suleimanov's research while affiliated with Russian Academy of Sciences and other places
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Publications (44)
The reaction of [2-(dimethylaminomethyl)]cymantrenyl]lithium with ytterbium diiodide affords [2-(dimethylaminomethyl)cymantrenyl]ytterbium iodide or bis[2-(dimethylaminomethyl)cymantrenyl]ytterbium depending on the ratio of the starting reactants. Reactions of these complexes with a series of electrophiles (H2O, Me3SiCl, MeCOCl, HgCl2, PhCOCl) were...
The interaction of (CO)3MnC5H3RLi (R=2-Me2NCH2, H) with 2-Ph-1-HgBr-1, 2-C2B10H10 and (1, 7-C2H2B10H9-9)TlCl2 gives the corresponding C-carboranylmercury and B-carboranylthallium derivatives with M-C bonds, in which the C atom belongs to the cyclopentadienyl ring of the substituted cymantrenyl fragment. The structures of the compounds obtained are...
The interaction of NaM(CO)5 (M=Mn, Re) with (m-H2C2B10H9-9)TlCl2 in THF yields the stable polymetallic chain compounds (m-H2C2B10H9-9)Tl(Cl)M(CO)5. The stability of the compounds obtained is compared to that of the analogous (B-carboranyl)mercury derivatives.
1.
The reactions of the metal carbonyl halides L(CO)mMX with lanthanides have been studied for the first time. It has been established that, depending on the condition and the type of the lanthanide, derivatives of the bivalent lanthanides L(CO)mMLnX (Ln=Sm, Yb) are formed or mixtures of mono- and disubstituted metal carbonyl derivatives of the lan...
The authors report preliminary results for previously unknown reactions of organic derivatives of divalent lanthanides such as RLnX (I), where Ln = Sm or Yb, R = Alk or AR and X is a halogen, with carbon monoxide. The reaction of (I) obtained in situ by the oxidative addition of RX to Ln/sup 0/ in THF with carbon monoxide at PCO from 10 to 25 atm l...
Alkyl and aryl iodides add to zero-valent lanthanides to form Grignard-like reagents RLnI. The authors have already studied the addition of Ln(0) at the Hg-I bond in HgIâ and RHgI compounds to give bimetallic derivatives of divalent lanthanides. In the present work, preliminary results are given for a study of the reactions of rare-earth elements w...
It has been shown that the reaction of amalgamated lanthanides (Ln) with binuclear carbonyls Co2(CO)8 and [CpMo(CO)3]2 in THF at room temperature leads, depending on the reagent ratio, to tris-(I) or bis- metal carbonyl(II) complexes of lanthanides, Ln[M(CO)mL]n (Ln = Sm, Yb; M(CO)mL = Co(CO)4, Mo(CO)3Cp; n = 2,3). II (Ln = Sm, Yb) may also be obta...
It has been established that the reaction of metallocyclopentadienyl mercurials with an excess of elemental lanthanides Ln(Ln = Sm, Eu, Yb) in tetrahydrofuran yields substituted cyclopentadienyl derivatives of the metals.
In the cases of a typical lanthanide (Sm) and atypical lanthanide (Yb), they have shown that activated metallic Sm and Yb react with free CO (p/sub CO/ = 20 atm) at 20/sup 0/C in THF to give carbonyl complexes Ln(CO)/sub m/(THF)/sub n/ (Ln = Sm and Yb) (I). Two bands (1995 and 2020 cm/sup -1/) are found in the IR spectra of solutions of (I) in THF...
The title compounds, Ln[PhCr(CO)3]2·n(tetrahydrofuran) Lu = Sm, Eu, Yb, representing a new type of organometallic derivative of divalent lanthanides, were produced by the reaction of Hg[PhCr(CO)3]2 with an excess of Ln0 filings in tetrahydrofuran.
The interaction of activated La powder with [CpMo(CO)3]2 or Hg[CpMo(CO)3]2 in THF resulted in the formation of crystalline (THF)5La[CpMo(CO)3]3 · THF (I), which oxidized readily on exposure to air with cleavage of [CpMo(CO)3)2. Complex I was characterized by X-ray structural analysis. The La atom is bound to three equivalent CpMo(CO)3 fragments via...
With the use of oxidative insertion of tin(II) acetylacetonate (acac) into mercuric derivatives of carboranes, new types of polymetallic chainlike compounds were obtained in which the acac ligands occupy cis positions on the tetravalent hexacoordinated tin. In was found that in benzene the insertion of Sn(acac)2 into unsymmetrical B-carboranylmercu...
The interaction of Yb0 with (C5H5FeC5H4)2Hg and [(OC)3MnC5H4]2 Hg in THF resulted in the formation of ferrocenyl and cymantrenyl derivatives of divalent ytterbium. Derivatives of the RLnI type may be obtained in low yields from the basis of ferrocene (cymantrenyl) iodides and Yb0 in THF. The structures of the resulting compounds were characterized...
Das Lithium-o-carboran (I) reagiert mit Diiodiden von Samarium, Europium und Ytterbium zu Grignard-ähnlichen Verbindungen (II), die mit Trimethylchlorsilan oder Acetylchlorid zu Carboranylsilanen oder Methylcarboranylketonen reagieren.
The first metal carbonyl derivatives, Ln[Co(CO)4]2·(THF)n(THF = tetrahydrofuran; n= 3,4), of divalent lanthanoids Ln(Ln = Sm, Eu, Yb) were prepared by treating Hg[Co(CO)4]2 with an excess of Sm, Eu, or Yb in THF at room temperature; the title complexes were also formed in high yields from the reaction of stoicheiometric amounts of the appropriate L...
Interaction of C-lithiumcarboranes with LnI2 (Ln = Sm, Eu, Yb) give compounds which react with trimethylchlorosilane or carboxylic acid chloroanhydride to give trimethylsilylcarboranes or carboranyl ketones. The carborane derivatives formed at the first stage can be assigned the composition RLnI similar to Grignard reagents. The compounds prepared...
Carboranyl derivatives of lanthanides have been prepared by interaction of the lithium derivatives of carboranes with the salts LnCl3 · nTHF (Ln = La, Tm, Yb). The influence of the ratio of the reagents, the type of metal and the nature of solvents on these reactions has been studied.
1.
The reaction of ytterbium(O) with C5H5HgI, CF3HgI, and HgI2 in THF gives unstable adducts, which are demercurated if they are kept in the reaction mixture or if the temperature is raised.
2.
The theory was expressed that these adducts are formed mainly by insertion of the lanthanide(O) across the Hg-I bond.
It has been shown that the interaction of C- and B-mercurocarboranes with lanthanides (La, Tm, Yb) in THF at 20°C give carboranyl derivatives of lanthanides in which the lanthanides are linked with the carborane nuclei via CLn or BLn bonds.
The interaction of (C5H5)2Hg with activated Lno, where Ln La, Sm, Eu, Tm, Yb, in THF was shown to give either divalent or trivalent cyclopentadienyl derivatives of these metals, depending on the reaction conditions and re-agents ratio.
1.
The oxidative insertion of tin(n) acetylacetonate into the B-Hg bond of B-mercurated carboranes, leading to bimetallic compounds with a Hg-Sn bond, has been realized for the first time.
Conclusions Conditions were developed for obtaining thea-metallocenylglycolic acids of the ferrocene and cymantrene series from the corresponding aldehydes under interphase catalysis conditions.
The molecular structures of the L-menthyl ester of S-α-bromomercuriphenyl-acetic acid, diastereomer II, [α]20D −18°, and of the related L-menthyl ester of α-bromobis(triphenylphosphine)platinummeruriphenylacetic acid, VI, have been investigated by the X-ray method. Insertion of L2Pt carbenoid appears to occur into the HgBr bond in II and two phosp...
A new experimental procedure for isolation of L-menthyl esters of α-bromo mercuryphenylacetic acid as almost pure diastereoisomers I, [α]20D -- 132° and II, [α]20D -- 18° is reported. Related dialkylmercuries R2Hg III, [α]20D − 32°, and IV, [α]20D − 5°, were prepared. Absolute configurations of benzylic chiral carbon are assigned from ORD curves (R...
Conclusions 1.Some mono- and bisester and amide derivatives of metalcarboxylic acids of platinum and palladium were prepared via the organomercury compounds.2.The compound R2NCO-Hg-Pt(Ph3P)2-CONR2, in which the metalcarboxylic acid fragment is coupled with the metal-metal bond, was obtained for the first time.
1.
The diastereomers of the L-menthyl esters of α-bromomercuri-phenylacetic acid were obtained with a diastereomeric purity of 94–100%.
2.
It was shown that the PMR method (δ,2JH-Hg) can be used to determine the diastereomeric composition of mixtures of organomercury compounds of type R2Hg and RHgBr.
3.
In deuterobenzene the protons of the HCHgCH f...
The reaction between (Ph3P)3Pt0 and diastereoisomeric L-menthyl esters of α-bromomercuriphenylacetic acid or related R2Hg compounds has been investigated. The preparation of σ-organomercuryplatinum and corresponding σ-organoplatinum derivatives is reported. Diastereomer RHgBr (I), [α]20D −120°, and diastereomer II, [α]20D −18°, afforded σ-organopla...
1.
The fragmentation of cycloalkyl platinum-mercury compounds under the action of Ph3C+− BF
4
−
has been studied.
Conclusions The insertion of Pt(0)(PPh3)2 across the carbon-metal bond in mercury derivatives of cyclopentadienylmanganese tricarbonyl and cyclopentadienylrhenium tricarbonyl leads to compounds with a mercury-platinum bond, the dimercuration of which gives thes-platinum derivatives of thesep complexes.
1.
The stability of tetrahydrofuran solutions of lithiocyclopentadienyltricarbonylmanganese and lithiocyclopentadienyltricarbonylrhenium has been investigated.
2.
The previously unknown tertiary alcohols (OC)3MnC5H4C(CH3)(OH)C5H4Mn(CO)3 and (OC)3MnC5H4C·(CH3)(OH)C5H4Re(CO)3 have been synthesized.
Die Einschiebungsreaktion des Hg-Fe-Komplexes (I) mit Tris-[triphenylphosphin]-Pt(O) (II) f?hrt bei niedriger Temp. zu dem Produkt (III).
1.
The reaction of cycloalkylmercuric bromides with Pt(PPh3)3 involves the intermediacy of compounds with an Hg-Pt bond, which can be isolated in the dark at low temperatures (0–10C).
2.
Photolysis of the platinum mercury compounds in solution forms (-cycloalkyl)bis(triphenylphosphine)-platinum bromides. These are the first reported -platinum deriv...
The mercuration of cyclopentadienyl(triphenylphosphine)manganese or rhenium dicarbonyl gave some new organomercury derivatives, which when reacted in known manner with Pt(PPh3)3 in THF were converted to the corresponding s-platinum derivatives.
It was discovered that the mercury halides of the cyclopentadienyl derivatives of manganese and rhenium carbonyls react with tris(triphenylphosphine)platinum to give new complexes with a platnium-carbon s-bond.
The direct metallation of manganese and rhenium cyclopentadienyltricarbonyl complexes by the action of PhYbI was studied. The metallation of the manganese complex with PhYbI leads to the formation of the Grignard-like compound (CO)âMnCâHâYbI. The rhenium complex is not metallated by the action of PhYbI.
The reaction of (CâHâ)âHg and zero-valent lanthanides are discussed. Di reactions of the different Ln(O) metals are discussed (Ln = La, Sm, Tm, Yb, and Eu).
The reactions of YbI x 4THF with cymanthenyllithium and with cymanthenylmercury iodide lead to the formation of the corresponding ytterbium(II) and ytterbium(III) derivatives respectively. By means of ¹H and ¹³C NMR spectroscopy it was shown that the introduction of the substituents Yb/sup II/ and Yb/sup II/CâHâMn(CO)â into the cyclopentadienyl...
Citations
... 69: Infinite 1D chain structure of chain 2 in 22b with 2 isocarbonyl linkages. ...
... This initial report was followed by many others from different laboratories. The most common reactions involving transition-metal carbonyl complexes and rare-earth reagents include a) salt elimination from alkali metal or thallium carbonylmetallates and (partly substituted and/or solvated) rare-earth halides, [68] b) transmetalation as in the example stated above, [67,69] c) oxidative www.chemeurj.org addition of rare earths or their amalgams to transition-metal carbonyl halides, [70] and d) reduction of (partly substituted) transition-metal carbonyls with rare-earths or their amalgams. ...
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... This initial report was followed by many others from different laboratories. The most common reactions involving transition-metal carbonyl complexes and rare-earth reagents include a) salt elimination from alkali metal or thallium carbonylmetallates and (partly substituted and/or solvated) rare-earth halides, [68] b) transmetalation as in the example stated above, [67,69] c) oxidative www.chemeurj.org addition of rare earths or their amalgams to transition-metal carbonyl halides, [70] and d) reduction of (partly substituted) transition-metal carbonyls with rare-earths or their amalgams. ...
... As discussed above, the two carbon vertices in dicarba-closo-dodecarboranes bear relatively acidic hydrogen atoms, which are readily replaced by metals or organic groups. 20,21 Besides, substituents can also be introduced with good control to at least a certain number of boron vertices, making the research in this area very versatile and attractive for BNCT. The icosahedral closo-C 2 B 10 H 12 carborane 22 and metallacarborane 23 [M(C 2 B 9 H 11 ) 2 ] À clusters are 3D aromatic moieties, possessing high symmetry and stability, 24 and generally low cytotoxicity, 25,26 being good candidates for BNCT. ...
