CCL

Összesen 8 találat.
#/oldal:
Részletezés:
Rendezés:

1.

001-es BibID:BIBFORM085363
Első szerző:Jószai Róbert (vegyész)
Cím:Metal-metal bond or isolated metal centers? : Interaction of Hg(CN)2 with square planar transition metal cyanides / Róbert Jószai, Imre Beszeda, Attila C. Bényei, Andreas Fischer, Margit Kovács, Mikhail Maliarik, Péter Nagy, Andrey Shchukarev, Imre Tóth
Dátum:2005
ISSN:0020-1669 1520-510X
Megjegyzések:Three adducts have been prepared from Hg(CN)2 and square planar MII(CN)42- transition metal cyanides (M ) Pt, Pd, or Ni, with d8 electron shell) as solids. The structure of the compounds K2PtHg(CN)6?2H2O( 1), Na2PdHg(CN)6?2H2O( 2), and K2NiHg(CN)6?2H2O( 3) have been studied by single-crystal X-ray diffraction, XPS, Raman spectroscopy, and luminescence spectroscopy in the solid state. The structure of K2PtHg(CN)6?2H2O consists of one-dimensional wires. No CN- bridges occur between the heterometallic centers. The wires are strictly linear, and the Pt(II) and Hg(II) centers alternate. The distance d Hg-Pt is relatively short, 3.460 ?A. Time-resolved luminescence spectra indicate that Hg(CN)2 units incorporated into the structure act as electron traps and shorten the lifetime of both the short-lived and longer-lived exited states in 1 compared to K2[Pt(CN)4]?2H2O. The structures of Na2PdHg(CN)6?2H2O and K2NiHg(CN)6?2H2O can be considered as double salts; the lack of heterometallophilic interaction between the remote Hg(II) and Pd(II) atoms, d Hg-Pd ) 4.92 ?A, and Hg(II) and Ni(II) atoms, d Hg-Ni ) 4.61 ?A, is apparent. Electron binding energy values of the metallic centers measured by XPS show that there is no electron transfer between the metal ions in the three adducts. In solution, experimental findings clearly indicate the lack of metal?metal bond formation in all studied HgII?CN-?MII(CN)42- systems (M ) Pt, Pd, or Ni).
Tárgyszavak:Természettudományok Kémiai tudományok idegen nyelvű folyóiratközlemény külföldi lapban
folyóiratcikk
Megjelenés:Inorganic Chemistry. - 44 : 26 (2005), p. 9643-9651. -
További szerzők:Beszeda Imre (1966-) (okl. anyagtudományi mérnök-fizikus) Bényei Attila (1962-) (vegyész) Fischer, Andreas Kovács Margit Maliarik, Mikhail Nagy Péter (1976-) (vegyész) Shchukarev, Andrey Tóth Imre (1950-) (vegyész)
Pályázati támogatás:T038296
OTKA
T043365
OTKA
Internet cím:Szerző által megadott URL
DOI
Intézményi repozitóriumban (DEA) tárolt változat
Borító:

2.

001-es BibID:BIBFORM006208
Első szerző:Maliarik, Mikhail
Cím:Photoinduced electron transfer via nonbuttressed metal-metal bonds : the photochemical study of binuclear complexes with platinum-thallium bonds / Maliarik, M., Plyusnin, V. F., Grivin, V. P., Toth, I., Glaser, J.
Dátum:2008
ISSN:1089-5639
Megjegyzések:The photochemistry of binuclear metal-metal bonded complexes [(NC)(5)Pt-Tl(solv)(x)] (solv is water or dimethylsulfoxide) has been studied in aqueous and dimethylsulfoxide solutions. Both stationary and nanosecond laser flash photolysis have been carried out on the species. The metal-metal bonded complexes have been photolyzed by irradiation into the corresponding intense MMCT absorption bands. Photoexcitation results in the cleavage of the platinum-thalliurn bond and the formation of a solvated thallous ion and a cyano complex of platinum(IV), [Pt(CN)(5)(Solv)](-), in both cases. The species have been characterized by multinuclear NMR and optical spectroscopy. The products of the photoreaction indicate a complementary two-electron transfer occurring between platinum and thallium ions in the binuclear Pt-T1 species. Quantum yield values for the photodecomposition of the species have been determined. The intermediates of the photoinduced metal-to-metal electron transfer have been detected and characterized by optical spectroscopy. The kinetics of transient formation and decomposition have been studied, and mechanisms of the photoactivated redox reaction have been suggested.
Tárgyszavak:Természettudományok Kémiai tudományok idegen nyelvű folyóiratközlemény külföldi lapban
Megjelenés:Journal of Physical Chemistry. A. - 112 : 26 (2008), p. 5786-5793. -
További szerzők:Plyusnin, Victor F. Grivin, Vjacheslav P. Tóth Imre (1950-) (vegyész) Glaser, Julius
Internet cím:elektronikus változat
elektronikus változat
Borító:

3.

001-es BibID:bibEBI00008446
Első szerző:Maliarik, Mikhail
Cím:New class of oligonuclear platinum-thallium compounds with a direct metal-metal bond. 2. : Structural characterization of the complexes / M. Maliarik, K. Berg, J. Glaser, M. Sandström, I. Tóth
Dátum:1998
ISSN:0020-1669
Megjegyzések:A new series of four binuclear platinum?thallium cyano compounds containing a direct and unsupported by ligands metal?metal bond has been prepared in aqueous solution. The structure of these compounds represented by the formula [(NC)5Pt?Tl(CN)n-1](n-1)- (n = 1?4 for compound I, II, III, and IV, respectively) was determined by means of multinuclear NMR (195Pt, 205Tl, 13C) supported by Raman spectroscopy. In addition, a trinuclear complex with the formula [(NC)5Pt?Tl?Pt(CN)5]3- is formed in solutions where the Pt/Tl ratio is larger than 1. The compounds exhibit very large one-bond 195Pt?205Tl spin?spin coupling constants, 25?71 kHz; the value for compound I, 71?060 Hz, is the largest reported coupling constant between two different nuclei. The possible reasons for this strong coupling, as well as its variation along the series of the binuclear compounds I?IV, are discussed in terms of the metal?metal bond strength, varying participation of s-electrons in this bond and oxidation state of the metal ions.
Tárgyszavak:idegen nyelvű folyóiratközlemény külföldi lapban
Megjelenés:Inorganic chemistry. - 37 : 12 (1998), p. 2910-2919. -
További szerzők:Berg, Katja E. Glaser, Julius Sandström, Magnus Tóth Imre (1950-) (vegyész)
Internet cím:DOI
Borító:

4.

001-es BibID:bibEBI00008447
Első szerző:Maliarik, Mikhail
Cím:New class of oligonuclear platinum-thallium compounds with a direct metal-metal bond. 3. : Unusual equilibria in aqueous solution / M. Maliarik, J. Glaser, I. Tóth, M. Silva, L. Zékány
Dátum:1998
Tárgyszavak:idegen nyelvű folyóiratközlemény külföldi lapban
Megjelenés:European Journal Of Inorganic Chemistry. - (1998), p. 565-570. -
További szerzők:Glaser, Julius Tóth Imre (1950-) (vegyész) Silva, Mateus Zékány László (1948-) (vegyész)
Borító:

5.

001-es BibID:BIBFORM105015
035-os BibID:(WOS)000186023900039 (Scopus)10744233745
Első szerző:Nagy Péter (vegyész)
Cím:Kinetics and mechanism of formation of the platinum-thallium bond: The [(CN)(5)Pt-Tl(CN)(3)](3-) complex / Péter Nagy, Imre Tóth, István Fábián, Mikhail Maliarik, Julius Glaser
Dátum:2003
ISSN:0020-1669 1520-510X
Tárgyszavak:Természettudományok Kémiai tudományok idegen nyelvű folyóiratközlemény külföldi lapban
folyóiratcikk
Megjelenés:Inorganic Chemistry. - 42 : 21 (2003), p. 6907-6914. -
További szerzők:Tóth Imre (1950-) (vegyész) Fábián István (1956-) (vegyész) Maliarik, Mikhail Glaser, Julius
Internet cím:Szerző által megadott URL
DOI
Intézményi repozitóriumban (DEA) tárolt változat
Borító:

6.

001-es BibID:BIBFORM085364
Első szerző:Nagy Péter (vegyész)
Cím:Solubility, Complex Formation, and Redox Reactions in the Tl2O3?HCN/CN-?H2O System. Crystal Structures of the Cyano Compounds Tl(CN)3·H2O, Na[Tl(CN)4]·3H2O, K[Tl(CN)4], and TlI[TlIII(CN)4] and of TlI2C2O4? / Péter Nagy, Andreas Fischer, Julius Glaser, Andrey Ilyukhin, Mikhail Maliarikm, Imre Tóth
Dátum:2005
ISSN:0020-1669 1520-510X
Megjegyzések:Thallium(III) oxide can be dissolved in water in the presence of strongly complexing cyanide ions. TlIII is leached from its oxide both by aqueous solutions of hydrogen cyanide and by alkali-metal cyanides. The dominating cyano complex of thallium(III) obtained by dissolution of Tl2O3 in HCN is [Tl(CN)3(aq)] as shown by 205Tl NMR. The Tl(CN)3 species has been selectively extracted into diethyl ether from aqueous solution with the ratio CN-/TlIII ) 3. When aqueous solutions of the MCN (M ) Na+,K +) salts are used to dissolve thallium(III) oxide, the equilibrium in liquid phase is fully shifted to the [Tl(CN)4]- complex. The Tl(CN)3 and Tl(CN)4- species have for the first time been synthesized in the solid state as Tl(CN)3?H2O( 1), M[Tl(CN)4] (M) Tl (2) and K ( 3)), and Na[Tl(CN)4]?3H2O (4) salts, and their structures have been determined by single-crystal X-ray diffraction. In the crystal structure of 1, the thallium(III) ion has a trigonal bipyramidal coordination with three cyanide ions in the equatorial plane, while an oxygen atom of the water molecule and a nitrogen atom from a cyanide ligand, attached to a neighboring thallium complex, form a linear O?Tl?N fragment. In the three compounds of the tetracyano?thallium(III) complex, 2?4, the [Tl(CN)4]- unit has a distorted tetrahedral geometry. Along with the acidic leaching (enhanced by TlIII?CN- complex formation), an effective reductive dissolution of the thallium(III) oxide can also take place in the Tl2O3?HCN?H2O system yielding thallium(I), while hydrogen cyanide is oxidized to cyanogen. The latter is hydrolyzed in aqueous solution giving rise to a number of products including (CONH2)2, NCO-, and NH4+ detected by 14N NMR. The crystalline compounds, TlI[TlIII(CN)4], TlI2C2O4, and (CONH2)2, have been obtained as products of the redox reactions in the system. Introduction In contrast to general assumptions based on the standard reduction potentials of the Tl3+/Tl+ (E? ) 1.25 V)1 and (CN)2/CN- or (CN)2/HCN (E? ) 0.27 and 0.37 V for CNand HCN, respectively)2,3a redox couples, it has been shown that thallium(III) forms kinetically stable cyanide complexes
Tárgyszavak:Természettudományok Kémiai tudományok idegen nyelvű folyóiratközlemény külföldi lapban
folyóiratcikk
Megjelenés:Inorganic Chemistry. - 44 : 7 (2005), p. 2347-2357. -
További szerzők:Fischer, Andreas Glaser, Julius Ilyukhin, Andrey Maliarik, Mikhail Tóth Imre (1950-) (vegyész)
Pályázati támogatás:T038296
OTKA
Internet cím:Szerző által megadott URL
DOI
Intézményi repozitóriumban (DEA) tárolt változat
Borító:

7.

001-es BibID:BIBFORM084873
Első szerző:Nagy Péter (vegyész)
Cím:Kinetics and Mechanism of Platinum-Thallium Bond Formation : The Binuclear [(CN)5Pt-Tl(CN)]- and the Trinuclear [(CN)5Pt-Tl-Pt(CN)5]3- Complex / Péter Nagy, Imre Tóth, István Fábián, Mikhail Maliarik, Julius Glaser
Dátum:2004
ISSN:0020-1669 1520-510X
Megjegyzések:Formation kinetics of the metal?metal bonded binuclear [(CN)5Pt?Tl(CN)]- (1) and the trinuclear [(CN)5Pt?Tl?Pt(CN)5]3- (2) complexes is studied, using the standard mix-and-measure spectrophotometric method. The overall reactions are Pt(CN)42- + Tl(CN)2+ ? 1 and Pt(CN)42- + [(CN)5Pt?Tl(CN)]- ? 2. The corresponding expressions for the pseudo-first-order rate constants are kobs = (k1[Tl(CN)2+] + k-1)[Tl(CN)2+] (at Tl(CN)2+ excess) and kobs = (k2b[Pt(CN)42-] + k-2b)[HCN] (at Pt(CN)42- excess), and the computed parameters are k1 = 1.04 ± 0.02 M-2 s-1, k-1 = k1/K1 = 7 x 10-5 M-1 s-1 and k2b = 0.45 ± 0.04 M-2 s-1, K2b = 26 ± 6 M-1, k-2b = k2b/K2b = 0.017 M-1 s-1, respectively. Detailed kinetic models are proposed to rationalize the rate laws. Two important steps need to occur during the complex formation in both cases:? (i) metal?metal bond formation and (ii) the coordination of the fifth cyanide to the platinum site in a nucleophilic addition. The main difference in the formation kinetics of the complexes is the nature of the cyanide donor in step ii. In the formation of [(CN)5Pt?Tl(CN)]-, Tl(CN)2+ is the source of the cyanide ligand, while HCN is the cyanide donating agent in the formation of the trinuclear species. The combination of the results with previous data predict the following reactivity order for the nucleophilic agents:? CN- > Tl(CN)2+ > HCN.
Tárgyszavak:Természettudományok Kémiai tudományok idegen nyelvű folyóiratközlemény külföldi lapban
folyóiratcikk
Megjelenés:Inorganic Chemistry. - 43 : 17 (2004), p. 5216-5221. -
További szerzők:Tóth Imre (1950-) (vegyész) Fábián István (1956-) (vegyész) Maliarik, Mikhail Glaser, Julius
Pályázati támogatás:OTKA T 038296
OTKA
OTKA M 028244
OTKA
Internet cím:Szerző által megadott URL
DOI
Intézményi repozitóriumban (DEA) tárolt változat
Borító:

8.

001-es BibID:BIBFORM018853
Első szerző:Purgel Mihály (vegyész)
Cím:Binuclear Pt-Tl Bonded Complex with Square Pyramidal Coordination around Pt : A Combined Multinuclear NMR, EXAFS, UV-Vis, and DFT/TDDFT Study in Dimethylsulfoxide Solution / Mihály Purgel, Mikhail Maliarik, Julius Glaser, Carlos Platas-Iglesias, Ingmar Persson, Imre Tóth
Dátum:2011
ISSN:0020-1669
Megjegyzések:The structure and bonding of a new Pt-Tl bonded complex formed in dimethylsulfoxide (dmso), (CN)4Pt?Tl(dmso)5+, have been studied by multinuclear NMR and UV?vis spectroscopies, and EXAFS measurements in combination with density functional theory (DFT) and time dependent density functional theory (TDDFT) calculations. This complex is formed following the equilibrium reaction Pt(CN)42? + Tl(dmso)63+ (CN)4Pt?Tl(dmso)5+ + dmso. The stability constant of the Pt?Tl bonded species, as determined using 13C NMR spectroscopy, amounts to log K = 2.9 ? 0.2. The (NC)4Pt?Tl(dmso)5+ species constitutes the first example of a Pt?Tl bonded cyanide complex in which the sixth coordination position around Pt (in trans with respect to the Tl atom) is not occupied. The spectral parameters confirm the formation of the metal?metal bond, but differ substantially from those measured earlier in aqueous solution for complexes (CN)5Pt?Tl(CN)n(H2O)xn? (n = 0?3). The 205 Tl NMR chemical shift, ? = 75 ppm, is at extraordinary high field, while spin?spin coupling constant, 1JPt?Tl = 93 kHz, is the largest measured to date for a Pt?Tl bond in the absence of supporting bridging ligands. The absorption spectrum is dominated by two strong absorption bands in the UV region that are assigned to MMCT (Pt-Tl) and LMCT (dmso ? Tl) bands, respectively, on the basis of MO and TDDFT calculations. The solution of the complex has a bright yellow color as a result of a shoulder present on the low energy side of the band at 355 nm. The geometry of the (CN)4Pt?Tl core can be elucidated from NMR data, but the particular stoichiometry and structure involving the dmso ligands are established by using Tl and Pt LIII-edge EXAFS measurements. The Pt?Tl bond distance is 2.67(1) Å, the Tl?O bond distance is 2.282(6) Å, and the Pt?C?N entity is linear with Pt?C and Pt???N distances amounting to 1.969(6) and 3.096(6) Å, respectively. Geometry optimizations on the (CN)4Pt?Tl(dmso)5+ system by using DFT calculations (B3LYP model) provide bond distances in excellent agreement with the EXAFS data. The four cyanide ligands are located in a square around the Pt atom, while the Tl atom is coordinated in a distorted octahedral fashion with the metal being located 0.40 Å above the equatorial plane described by four oxygen atoms of dmso ligands. The four equatorial Tl?O bonds and the four cyano ligands around the Pt atom are arranged in an alternate geometry. The coordination environment around Pt may be considered as being square pyramidal, where the apical position is occupied by the Tl atom. The optimized geometry of (CN)4Pt?Tl(dmso)5+ is asymmetrical (C1 point group). This low symmetry might be responsible for the unusually large NMR linewidths observed due to intramolecular chemical exchange processes. The nature of the Pt?Tl bond has been studied by MO analysis. The metal?metal bond formation in (CN)4Pt?Tl(dmso)5+ can be simply interpreted as the result of a Pt(5dz2)2 ? Tl(6s)0 donation. This bonding scheme may rationalize the smaller thermodynamic stability of this adduct compared to the related complexes with (CN)5Pt?Tl entity, where the linear C?Pt?Tl unit constitutes a very stable bonding system.
Tárgyszavak:Természettudományok Kémiai tudományok idegen nyelvű folyóiratközlemény külföldi lapban
Megjelenés:Inorganic Chemistry. - 50 : 13 (2011), p. 6163-6173. -
További szerzők:Maliarik, Mikhail Glaser, Julius Platas-Iglesias, Carlos Persson, Ingmar Tóth Imre (1950-) (vegyész)
Pályázati támogatás:OTKA 63388)
OTKA
Internet cím:Szerző által megadott URL
DOI
Intézményi repozitóriumban (DEA) tárolt változat
Borító:
Rekordok letöltése1 
Corvina könyvtári katalógus v8.2.27 © 2023 Monguz kft. Minden jog fenntartva.