Synthesis, structural and multinuclear natural abundance (13C, 31P, 195Pt) CP/MAS NMR studies of crystalline O,O′-dialkyldithiophosphate platinum(II) complexes

Иванов, А. В.; Луценко, И. А.; Иванов, М. А.; Герасименко, А. В.; Antzutkin, Oleg N.

doi:10.1134/s1070328408080058

Cited by 14 publications

(12 citation statements)

References 17 publications

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“…Pt NMR studies are still uncommon as these measurements are hampered by the very large shift range and concomitantly large chemical shift anisotropies/spans, combined with the moderate sensitivity of the 195 Pt nucleus. 14,15 The considerable significance of catalytic Pt means that much of the reported 195 Pt solid state NMR literature relates to materials used in these applications. [16][17][18][19][20][21] Previous work has shown that the characteristics of the 195 Pt NMR spectra are independent of support material,…”

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Characterisation of platinum-based fuel cell catalyst materials using 195Pt wideline solid state NMR

Rees

Orr

Barrett

et al. 2013

Phys. Chem. Chem. Phys.

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This study demonstrates the utility of the novel Field Sweep Fourier Transform (FSFT) method for acquiring wideline (195)Pt NMR data from various sized Pt nanoparticles, Pt-Sn intermetallics/bimetallics used to catalyse oxidative processes in fuel cell applications, and various other related Pt3X alloys (X = Al, Sc, Nb, Ti, Hf and Zr) which can facilitate oxygen reduction catalysis. The (195)Pt and (119)Sn NMR lineshapes measured from the PtSn intermetallic and Pt3Sn bimetallic systems suggest that these are more ordered than other closely related bimetallic alloys; this observation is supported by other characterisation techniques such as XRD. From these reconstructed spectra the mean number of atoms in a Pt nanoparticle can be accurately determined, along with detailed information regarding the number of atoms present effectively in each layer from the surface. This can be compared with theoretical predictions of the number of Pt atoms in these various layers for cubo-octahedral nanoparticles, thereby providing an estimate of the particle size. A comparison of the common NMR techniques used to acquire wideline data from the I = 1/2 (195)Pt nucleus illustrates the advantages of the automated FSFT technique over the Spin Echo Height Spectroscopy (SEHS) (or Spin Echo Integration Spectroscopy (SEIS)) approach that dominates the literature in this area of study. This work also presents the first (195)Pt NMR characterisation of novel small Pt13 nanoclusters which are diamagnetic and thus devoid of metallic character. This unique system provides a direct measure of an isotropic chemical shift for these Pt nanoparticles and affords a better basis for determining the actual Knight shift when compared to referencing against the primary IUPAC shift standard (1.2 M Na2PtCl6(aq)) which has a very different local chemical environment.

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confidence: 99%

Characterisation of platinum-based fuel cell catalyst materials using 195Pt wideline solid state NMR

Rees

Orr

Barrett

et al. 2013

Phys. Chem. Chem. Phys.

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“…Analysis of the obtained results indicates that the anisotropy parameters and the principal values of 31 P chemical shift tensors for all four states of the Dtph groups are qualitatively similar: in all cases, δ aniso is negative, while the η values reflect approximately equal contributions of the axially symmetric and rhombic components to the chemical shift tensors. Studies of mono , bi , tetra , hexa , and polynuclear diisopropyl dithiophosphate complexes of nickel(II) [10], cadmium [8], zinc [28,29], lead (II) [30,31], sil ver(I) [32], platinum(II) [33], and thallium(I) [34], which we carried out previously, demonstrated that irrespective of the chemical nature of the complexing agent, the δ aniso value for bridging Dtph ligands is always negative, i.e., the direction of the MAS NMR spectra is determined by the condition δ zz < δ yy , δ xx ; the modulus of δ aniso is usually well correlated with the S-P-S angle [28]. Thus, it is clear that all Dtph groups in the obtained gold complex occupy bridging positions.…”

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Binding of Au3+ from solutions by nickel(II) and cadmium diisopropyl dithiophosphates: MAS 31P NMR, structure and thermal behavior of the polynuclear complex [Au2{S2P(O-iso-C3H7)2}2] n

et al. 2012

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Previously [1][2][3][4][5], we studied the chemisorption properties of binuclear cadmium dialkyldithiocar bamate complexes, [Cd 2 {S 2 CNR 2 } 4 ] (R = C 4 H 9 , iso C 4 H 9 , iso C 3 H 7 and R 2 = (CH 2 ) 5 ) with respect to solutions of AuCl 3 in 2M HCl. A number of gold(III)-cadmium heteropolynuclear complexes, in particular, ([Au(S 2 CNR 2 ) 2 ] 2 [CdCl 4 ]) n (R = iso C 4 H 9 [1, 2], iso C 3 H 7 [3]), ([NH 2 (C 4 H 9 ) 2 ][Au{S 2 CN(C 4 H 9 ) 2 } 2 ][CdCl 4 ]) n [4] and polynuclear complexes ([Au(S 2 CNR 2 ) 2 ][AuCl 4 ]) n (R = C 4 H 9 , R 2 = (CH 2 ) 5 ) [5], were isolated from the sorption systems on a preparative scale as individual gold(III) containing species. The intricate supramo lecular structure and the thermal behavior of the iso lated compounds were studied. The results attest to good prospects of using complexes with dithio ligands as chemisorbents for binding noble metals from dilute process solutions and for waste water treatment to remove heavy metal cations. Therefore, it was of inter est to study the chemisorption properties of complexes with another type of dithio ligands: dialkyl dithiophos phate ions (RO) 2 P(S)S -.This work is concerned with the chemisorption interaction of freshly precipitated nickel(II) and cad mium diisopropyl dithiophosphate complexes,and [Cd 2 {S 2 P(O iso C 3 H 7 ) 2 } 4 ], with [AuCl 4 ] -in 2M HCl. It was found that binding of gold(III) from the solution is accompanied by its reduction to gold(I) as a result of oxidation of some Dtph groups to the corresponding disulfide. The polynuclear gold(I) complex [Au 2 {S 2 P(O iso C 3 H 7 ) 2 } 2 ] n (I) was isolated from the chemisorption Abstract-The paper deals with reactions of freshly precipitated diisopropyl dithiophosphate (Dtph) com plexes of nickel(II), [Ni{S 2 P(O iso C 3 H 7 ) 2 } 2 ] and cadmium, [Cd 2 {S 2 P(O iso C 3 H 7 ) 2 } 4 ], with the [AuCl 4 ] -in 2M HCl, resulting in gold transition from the solution to the precipitate as polymeric gold(I) diisopropyl dithiophosphate. The reduction of gold(III) to gold(I) noted in both cases is due to oxidation of the relevant part of the Dtph group to bis(O,O' di (iso) propoxythiophosphoryl) disulfide, (iso C 3 H 7 O) 2 P(S)S-S(S)P(O iso C 3 H 7 ) 2 . The polynuclear gold(I) complex [Au 2 {S 2 P(O iso C 3 H 7 ) 2 } 2 ] n (I) was isolated on a pre parative scale from the chemisorption system and studied by MAS 31 P NMR and X ray diffraction. The key structural unit of I is the non centrosymmetric binuclear molecule [Au 2 {S 2 P(O iso C 3 H 7 ) 2 } 2 ] in which the gold atoms are connected by two bridging Dtph groups. The structure contains two types of non equivalent binuclear molecules related as conformational isomers. Owing to the relatively weak Au-Au contacts, the neighboring binuclear [Au 2 {S 2 P(O iso C 3 H 7 ) 2 } 2 ] molecules are involved in an infinite polymeric chain with conformer alternation along the chain. To elucidate the conditions for the recovery of bound gold(I), the pre cipitates formed in the sorption systems were studied by simultaneous ther...

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“…Таким образом, возможно упрочнение координационной σ-связи, являющейся результатом донорно-акцепторного взаимодействия лиганда-донора с ионом металла-акцептора [10]. РСА комплексов Pt(II) [11][12][13][14][15][16] [24].…”

Section: Aralash Ligandli Komplekslarning Elektron Va Geometrik Tuzilunclassified

CONFIGURATION AND COMPETITIVE REACTIVITY OF LIGANDS IN MIXED LIGAND COMPLEXES OF DIALKYLDITIOPHOSPHATES AND AMINOBENBENZIMIDAZOLE (Part I: Au, Pt, Ag) AMINOBENBENZIMIDAZOLE (Part 2. Zn, Fe, Ni)

2020

Chemistry and Chemical Engineering

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With the aim of determination of electronic and geometrical structures of mixed-ligand complexes, theoretical modeling of the structures of coordination compounds of transition metals with dialkyldithiophosphate chelating ligands with aminobenzimidazoles carried out using quantum chemical methods. Using BIOVIA Materials Accelrys Studio 2017 software packages, the geometry, electron density distribution, and frontier orbitals calculated for the mixed ligand complexes of Au(III), Pt(II), Ag(I), Cu(II), Ni(II), Fe(III), which are necessary for understanding the electronic structure of coordination compounds with chelating ligands.

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Synthesis, structural and multinuclear natural abundance (13C, 31P, 195Pt) CP/MAS NMR studies of crystalline O,O′-dialkyldithiophosphate platinum(II) complexes

Cited by 14 publications

References 17 publications

Characterisation of platinum-based fuel cell catalyst materials using 195Pt wideline solid state NMR

Characterisation of platinum-based fuel cell catalyst materials using 195Pt wideline solid state NMR

Binding of Au3+ from solutions by nickel(II) and cadmium diisopropyl dithiophosphates: MAS 31P NMR, structure and thermal behavior of the polynuclear complex [Au2{S2P(O-iso-C3H7)2}2] n

CONFIGURATION AND COMPETITIVE REACTIVITY OF LIGANDS IN MIXED LIGAND COMPLEXES OF DIALKYLDITIOPHOSPHATES AND AMINOBENBENZIMIDAZOLE (Part I: Au, Pt, Ag) AMINOBENBENZIMIDAZOLE (Part 2. Zn, Fe, Ni)

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