Structural aspects of heterooligonuclear platinum clusters – distortion isomers

AbstractThis review covers 15 clusters of the compositions Pt3Re2, Pt2Os3, Pt3AgAu, Pt3Ir3, Pt2M4 (M=Ag or Pd), PtM5 [M=Ru (×2) or Os], Pt3Os4, Pt6Au2, Pt2Ru6, Pt3Ru6, Pt2Ru8, and PtAu9. Each of the cluster contains two crystallographically independent molecules that differ mostly by degree of distortion and are classical examples of distortion isomerism. Their structures are very complex. The inner coordination spheres about the metal atoms (Pt and M) are very complex as well. The clusters are rich in metal-metal bond distances with the shortest being 2.573 Å (Pt-Au), 2.615 (Pt-Pt), and 2.673 Å (Ru-Ru).

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Crystallographic and structural characterization of heterometallic platinum clusters Part VIII. Heteronona- and heterodecanuclear clusters

Open Chemistry ◽

10.1515/chem-2015-0053 ◽

2014 ◽

Vol 13 (1) ◽

Author(s):

Milan Melník ◽

Peter Mikuš ◽

Clive E. Holloway

Keyword(s):

Structural Characterization ◽

Structural Parameters ◽

Platinum Atom ◽

Metal Bond ◽

Metal Atoms ◽

Metal Metal ◽

Platinum Clusters ◽

Metal Composition ◽

Independent Molecules

AbstractThis 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.

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Structural aspects of heterotrinuclear Pt2M, PtM2, and PtMM′ complexes – distortion isomers

Reviews in Inorganic Chemistry ◽

10.1515/revic-2017-0011 ◽

2018 ◽

Vol 38 (4) ◽

pp. 151-162 ◽

Cited By ~ 1

Author(s):

Milan Melnik ◽

Peter Mikus ◽

Andrea Forgacsova ◽

Maria Bodnar Mikulova

Keyword(s):

Structural Parameters ◽

Bond Angles ◽

Metal Atoms ◽

Metal Metal ◽

Coordination Spheres ◽

Independent Molecules ◽

Structural Aspects ◽

Metal Ligand ◽

Ligand Bond

AbstractIn this review, the structural parameters of 18 heterotrinuclear Pt2M (M=Hg, Zn, Cd, Au, Mn, Ag, Pd), PtM2 (M=Al, Ga, Sb, In, Mo, Fe), PtFeMn, PtHgMn, and PtFeOs types are summarized and analyzed. The Pt atoms are four-, five-, and even six-coordinated, among which the four-coordinated ones are the most common. The M atoms are found to be two- (Hg), three- (Hg), four- (Hg, Sb, In, Ag, Au), and six- (Ga, In, Al, Mo, Mn, Fe, Pd) coordinated and even sandwiched (FeC10). There is a wide variety of donor atoms (ligands) (O+NL, N+CL, NL, CO, CN, CL, Cl, SL, PL, I), which build up the respective inner coordination spheres about the metal atoms. The 17 complexes contain two crystallographically independent molecules within the same crystal, and 1 complex contains four such molecules. In each complex, the respective molecules are differing mostly by the degree of distortion in metal-metal and metal-ligand bond distances and ligand-metal-ligand bond angles, and are examples of distortion isomerism.

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Structural aspects of heterotetranuclear platinum clusters-distortion isomers

Reviews in Inorganic Chemistry ◽

10.1515/revic-2018-0006 ◽

2018 ◽

Vol 38 (2) ◽

pp. 77-86 ◽

Cited By ~ 2

Author(s):

Milan Melník ◽

Peter Mikuš

Keyword(s):

Membered Ring ◽

Metal Atoms ◽

Platinum Clusters ◽

Independent Molecules ◽

Structural Aspects

AbstractThis review includes 16 examples of distortion isomers of heterotetranuclear platinum clusters. The clusters are of the compositions: Pt3Sn, Pt2M2 (M=Au, Ag, W, Mo), and PtM3 (M=Os, Ru, Re). The four metal atoms are found in a distorted tetrahedral core (most common), planar-rhombohedral, spiked-triangular, and eight-membered ring skeleton. There are three pairs (Pt2W2, Pt2Au2, and Pt2Ag2) of clusters and all remainder clusters contain two crystallographically independent molecules within the same crystal. All are classical examples of distortion isomerism. Their structures are analyzed and discussed.

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Distortion isomers of PtM, Pt2M, PtM2 and PtMM′ (M = non-transition metals) derivatives-structural aspects

Main Group Metal Chemistry ◽

10.1515/mgmc-2017-0046 ◽

2018 ◽

Vol 0 (0) ◽

Author(s):

Milan Melník ◽

Peter Mikuš

Keyword(s):

Transition Metals ◽

Structural Parameters ◽

Bond Angles ◽

Bond Lengths ◽

Metal Atoms ◽

Independent Molecules ◽

Structural Aspects

Abstract An analysis of the structural parameters of PtM, Pt2M, PtM2 and PtMM′ (M = non-transition metals) derivatives shows that each complex contains two crystallographically independent molecules within the same crystal. The respective molecules differ by the degrees of distortion and exemplify the distortion isomerism. These are discussed in terms of the coordination with the platinum and the M atoms and the correlations are drawn among the metal atoms, donor atoms, bond lengths and bond angles. A wide variety of non-transition metals (Sn, Ga, In, Tl, Zn, Cd, Hg, Sb) exist, among which the most prevalent is Sn.

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Faculty Opinions recommendation of RNA-mediated metal-metal bond formation in the synthesis of hexagonal palladium nanoparticles.

Faculty Opinions – Post-Publication Peer Review of the Biomedical Literature ◽

10.3410/f.1018835.214450 ◽

2004 ◽

Author(s):

Andrew Ellington

Keyword(s):

Palladium Nanoparticles ◽

Bond Formation ◽

Metal Bond ◽

Metal Metal

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Ligand isomerism in Pt(II) complexes – structural aspects

Reviews in Inorganic Chemistry ◽

10.1515/revic-2020-0023 ◽

2021 ◽

Vol 0 (0) ◽

Author(s):

Milan Melník ◽

Peter Mikuš

Keyword(s):

Mixed Ligand ◽

Bidentate Ligands ◽

Trans Isomers ◽

Mean Values ◽

Bite Angle ◽

Coordination Spheres ◽

Structural Aspects

Abstract This review has focused on ligand isomers in Pt(II) complexes. There are a variety of inner coordination spheres about the platinum(II) atom (PtN4, PtN2Cl2, PtP2Cl2, PtPNC2, PtPNCl2, PtP2CBr, PtP2CS), build up by mono- and bidentate ligands. The bidentate ligands create a variety of metallocyclic rings. The L–Pt–L bite angle (mean values) open in the sequence: 73.1° (PNP) < 78.7° (NC2C) < 80.4° (NC2N) < 86.4° (PC2P) < 86.7° (PNNP) < 93.0° (CC3S). There are three types of isomers: ligand, mixed – (ligand + distortion), and mixed – (ligand + cis-trans), isomers, which are rarity.

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