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Crystallographic and structural characterization of heterometallic platinum compounds Part VII. Heterohepta- and heterooctanuclear clusters

100%
Melnik M., Mikuš P., Holloway C. E.
Open Chemistry
|
2015
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vol. 13
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issue 1
EN
This review classifies and analyzes over fifty heterohepta- and heterooctanuclear platinum clusters. There are eight types of metal combinations in heteroheptanuclear: Pt6M, Pt5M2, Pt4M3, Pt3M4, Pt2M5, PtM6, Pt3Hg2Ru2 and Pt2Os3Fe2. The seven metal atoms are in a wide variety of arrangements, with the most common being one in which the central M atom (mostly M(I)) is sandwiched by two M3 triangles. Another arrangement often found is an octahedron of M6 atoms asymmetrically capped by an M atom. The shortest Pt-M bond distances (non-transition and transition) are 2.326(1) Å (M = Ga) and 2.537(6) Å (M = Fe). The shortest Pt-Pt bond distance is 2.576(2) Å. In heterooctanuclear platinum clusters there are eight types of metal combinations: Pt6M2, Pt4M4, Pt3Ru5, Pt2M6, PtM7, Pt2W4Ni2, PtAu6Hg and PtAu5Hg2. From a structural point of view, the clusters are complex with bicapped octahedrons of eight metal atoms prevailing. The shortest Pt-M bond distances (non-transition and transition) are 2.651(3) Å (M = Hg) and 2.624(1) Å (M = Os). The shortest Pt-Pt bond distance is 2.622(1) Å. These values are somewhat longer than those in the heteroheptanuclear clusters. Several relationships between the structural parameters were found, and are discussed and compared with the smaller heterometallic platinum clusters
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Crystallographic and structural characterization of heterometallic platinum clusters Part VIII. Heteronona- and heterodecanuclear clusters

100%
Melník M., Mikuš P., Holloway C. E.
Open Chemistry
|
2015
|
vol. 13
|
issue 1
EN
This review classifies and analyses fifty heteronona- and heterodecanuclear Pt clusters of metal composition: Pt4Ru5, Pt3Ru6, Pt20sr PtRh8, PtAu8; Pt6M4, Pt5M5, Pt4M6, Pt3M2, Pt2M8, PtM9, Pt3Ru6M and PtAu8M. There are nine different heterometals: M = Ru, Au, Ag, Cu, Hg, Os, Rh, Ir and Fe, of which Ru and Au are the most frequent. The clusters crystallize mostly into two crystal classes, monoclinic (74%) and triclinic (18%), and their structures are complex. Three triangular layers of nine metal atoms arranged in the form of a face-shared bioctahedron are common in the series of heterononanuclear clusters. In the series of heterodecanuclear clusters distorted skeletal icosahedrons, where a central platinum atom is surrounded by nine metal atoms, and face (edge) shared (fused) bioctahedral cluster of the metal atoms are the most common. The most frequent ligands are CO and PPh3. The shortest metal-metal bond distances are: 2.540(4) Å (Pt-Fe), 2.580(2) Å (Ru-Ru), 2.584 Å (Pt-Pt) and 2.629(4) Å (Cu-Au). Several relationships between the structural parameters were found and are discussed. Some clusters contain two crystallographically independent molecules within the same crystal and are examples of distortion isomerism.
3
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Crystallographic and structural characterization of heterometalic platinum complexes Part X. Heteropolynuclear pt complexes

100%
Melník M., Mikuš P., Holloway C. E.
Open Chemistry
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2015
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vol. 13
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issue 1
EN
This review covers heteropolynuclear platinum complexes. There are over sixty examples with heterometal atoms as partners including non- transition metals, K, Cs, Mg, Ca, Sr, Tl, Sn, Pb, Zn, Cd, and transition metals: Cu, Ag, Fe, Co, Ni, Rh and Pd. In addition, there are examples for the lanthanides, Eu and Yb. The most common are Ag (x16) and K (x14). The predominant geometries for Pt(II) is square-planar and for Pt(IV) is octahedral. The overall structures are complex. In spite of the wide variety of heterometal atoms partners of platinum, there is “real” Pt-M bonds only with silver, ranging from 2.678 to 2.943(I) Å (ave 2.855 Å). The mean Pt-Pt bond distance is 2.869 Å.
4
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Crystallographic and structural characterization of heterometallic platinum clusters. Part IX. Heterooligonuclear Pt clusters

100%
Melník M., Mikuš P., Holloway C. E.
Open Chemistry
|
2015
|
vol. 13
|
issue 1
EN
This review classifies and analyzes over thirty heterooligonuclear platinum clusters with a wide variety of metal frameworks, from twelve to forty-four. There are thirteen heterometals (Ge, Sn, Hg, W, Mo, Ru, Rh, Pd, Os, Ni, Cu, Ag, Au) which are the partners of platinum. The clusters mostly crystallize in monoclinic (36,4%) and triclinic (30,3%) crystal classes. Their structures are complex, with platinum most commonly preferring interstitial sites, such as the centroids of icosahedrons. There are examples of distortion isomerism. The most common ligands are CO and PPh3, and it is interesting that the mean Pt-CO and M-CO bond distances are identical at 1.84 Å. In contrast, the mean Pt-μCO and M-μCO are of values of 2.02 and 1.97 Å, respectively, while the Pt-PPh3 and M-PPh3 bond distances are 2.30 and 2.28 Å, respectively. The shortest Pt-Pt, Pt-M (non-transition) and Pt-M (transition) bond distances are 2.559(2) Å, 2.412(2) Å (M = Ge) and 2.510(2) Å (M = Ni).
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