Synthesis and structural characterization of platinum carbonyl cluster dianions bis,tris,tetrakis, or pentakis(tri-.mu.2-carbonyl-tricarbonyltriplatinum)(2-). New series of inorganic oligomers

Calabrese, Joseph C.; Dahl, Lawrence F.; Chini, P.; Longoni, Giuliano; Martinengo, Secondo

doi:10.1021/ja00815a050

Cited by 269 publications

(167 citation statements)

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“…The first peak at the closest distance (not corrected from the phase shift) of 1.5 Å is attributed to the bond with a light atom, (carbon or oxygen). Such a peak is also present in the reference K 2 Pt-(CN) 4 . The second main peak at 2.4 Å is found to be the sum of several components, the major one arising from the existence of Pt-Pt bonds at 2.68 Å. Noteworthy is that the distance at 3.0 Å of the intertriangular Pt-Pt distance is not observed.…”

Section: Methodsmentioning

confidence: 56%

“…Figure 5 shows the FT modules of samples corresponding to the clusters Pt n,CO prepared at higher Pt concentration and deposited on carbon. The most important contribution is positioned at 1.5 Å, with an amplitude similar to the amplitude relative to the reference K 2 Pt(CN) 4 . In addition, a small contribution is measured that is assigned to Pt-Pt bonds.…”

Section: [Pt 3 (Co)mentioning

confidence: 70%

“…Fitting parameters (N, coordination number for absorber-backscatterer pair; R, absorber-backscatterer distance; σ, Debye-Waller factor; ∆E, correction of threshold energy; F, residue value) for the references are listed in Table 2. Figure 2 shows comparisons between calculated and experimental EXAFS function and FT modules of K 2 Pt(CN) 4 . Multiple Scattering Considerations.…”

Section: Methodsmentioning

confidence: 99%

“…Since then, several methods for preparing such supported catalysts have been proposed. As shown by X-ray diffraction crystal analysis, the Chini clusters display a twisted prismatic structure composed of n stacking triangular units stabilized by CO ligands 4 (atomic distances are indicated in Figure 1) and doubly negative charge as a whole. Their electronic structures have been theoretically studied.…”

Section: Introductionmentioning

confidence: 93%

“…Among them, supported [Pt 3 (CO) 6 ] n 2-clusters were soon recognized as very attractive materials. [4][5][6] They were first synthesized by Chini et al 4,5 in methanol or tetrahydrofuran (THF) solution by the reduction of Pt IV chloride in basic solution in the presence of carbon monoxide. Since then, several methods for preparing such supported catalysts have been proposed.…”

Section: Introductionmentioning

confidence: 99%

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Structural Characterization of Supported Platinum Carbonyl Clusters by X-ray Absorption Spectroscopy

et al. 2000

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The Chini-type Pt carbonyl clusters ([Pt 3 (CO) 6 ] n 2-, n ) 4, 5, 6) and other CO-stabilized Pt clusters were synthesized by γ-radiolysis, and their structures, when supported on carbon and R-alumina, were investigated by X-ray absorption spectroscopy (XAS). It was found that the stacking prismatic structure of triangular units in Chini clusters was transformed, when supported on carbon, into another structure in which the trimeric units are conserved but are now arranged in a planar monolayer. Some carbonyl groups remain to be ligated to Pt atoms under nitrogen atmosphere. However, on contact with the air, the carbonyl clusters are partially transformed into fcc Pt clusters. When supported on R-alumina, a more important structural evolution of supported clusters with a size growth is observed. Two groups of platinum clusters are obtained: the first one with a Pt-Pt distance corresponding to the intratriangular distance present in the Chini clusters, and the second one constituted of larger fcc clusters with a Pt-Pt distance close to the bulk one.

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Section: Methodsmentioning

confidence: 56%

Section: [Pt 3 (Co)mentioning

confidence: 70%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 93%

Section: Introductionmentioning

confidence: 99%

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Structural Characterization of Supported Platinum Carbonyl Clusters by X-ray Absorption Spectroscopy

et al. 2000

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Carbonyls

Wagner¹,

Kaesz²

2000

Kirk-Othmer Encyclopedia of Chemical Technology

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Carbon monoxide forms a host of metal carbonyl complexes, at least one for every transition metal. Mononuclear, polynuclear, and heteronuclear metal carbonyls are all known. The complexes, of general formula M x (CO) y , may be charged or neutral; the metal or metals are in the zero oxidation state. Metal carbonyls are useful as reagents and catalysts in organic synthesis, and play a role in both the Reppe and the oxo processes, as well as in the preparation of synthetic fuels and in vapor deposition of purified metals. The structure and bonding of the metal carbonyls, including that of cluster compounds, follow well‐defined rules. Synthesis of the metal carbonyls usually proceeds either from the reduction of the corresponding metal, initially in the form of a metallic salt, or via condensation of lower molecular weight compounds.

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Metal Carbonyls

McIndoe

Dyson

2003

Kirk-Othmer Encyclopedia of Chemical Technology

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Carbon monoxide forms a host of metal carbonyl complexes, at least one for every transition metal. Mononuclear, polynuclear, and heteronuclear metal carbonyls are all known. The complexes, of general formula M x (CO) y , may be charged or neutral; the metal or metals are in low, zero, or negative oxidation states. Synthesis of the metal carbonyls usually proceeds either from the reduction of the corresponding metal salt, although direct reaction between the metal and CO takes place for certain elements. Clusters are usually made via condensation of lower molecular weight compounds. The structure and bonding of the metal carbonyls, including those of cluster compounds, follow well‐defined rules. Metal carbonyls are extremely useful as reagents in organic synthesis and catalysts, playing a pivotal role in both the Reppe and the oxo processes, as well as in the preparation of fine chemicals.

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Synthesis and structural characterization of platinum carbonyl cluster dianions bis,tris,tetrakis, or pentakis(tri-.mu.2-carbonyl-tricarbonyltriplatinum)(2-). New series of inorganic oligomers

Abstract: small difference between the solvolysis rates of system 2 and the corresponding fluorenylidene derivatives78 argues against high contribution of this effect.

Cited by 269 publications

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Structural Characterization of Supported Platinum Carbonyl Clusters by X-ray Absorption Spectroscopy

Structural Characterization of Supported Platinum Carbonyl Clusters by X-ray Absorption Spectroscopy

Carbonyls

Metal Carbonyls

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