Platinum organometallic compounds: classification and analysis of crystallographic and structural data of monomeric five and higher coordinated

2013 ◽  
Vol 33 (1) ◽  
pp. 13-103 ◽  
Author(s):  
Milan Melník ◽  
Peter Mikuš ◽  
Clive Eduard Holloway
Keyword(s):  
Organometallic Compounds ◽  
Structural Data ◽  
Oxidation States ◽  
Trans Effect ◽  
Trigonal Bipyramidal ◽  
Square Planar ◽  
Coordination Spheres ◽  
Organoplatinum Compounds

AbstractFour hundred and twenty monomeric organoplatinum compounds, in which platinum atoms are five- and higher coordinated, are analyzed. The platinum atoms are found in the oxidation states +2, +3 and +4. The Pt(II) compounds by far prevail. There are wide varieties of the inner coordination spheres about the platinum centers. The Pt(II) compounds are five-coordinated (trigonal bipyramidal and square pyramidal), six-coordinated (different degrees of distortion), seven-coordinated (pentagonal bipyramidal, piano stool) and sandwiched (PtC10). The Pt(III) compound is square-planar. The Pt(IV) compounds are six- and eight-coordinated. There are several relationships between the Pt-L bond distances, covalent radii of the coordinated atom/ligand, and metallocycles, which are discussed. The trans-effect plays an important role in the inner coordination spheres about the Pt centers, especially on the Pt-L bond distances.

Platinum organometallic complexes: classification and analysis of crystallographic and structural data for dimeric complexes

2014 ◽  
Vol 34 (1) ◽  
pp. 25-90 ◽  
Author(s):  
Milan Melník ◽  
Peter Mikuš ◽  
Clive Edward Holloway
Keyword(s):  
Mixed Valence ◽  
Bond Distance ◽  
Structural Data ◽  
Organometallic Complexes ◽  
Oxidation States ◽  
Trigonal Bipyramidal ◽  
Dimeric Complexes ◽  
Square Planar ◽  
Distorted Octahedral ◽  
The Mean

AbstractThis review covers over 260 examples of dimeric organoplatinum complexes. Platinum is predominantly found in the oxidation states +2 and +4, but with some examples of 0, +1, +2.5, +3, and of mixed-valence as well. A number of coordination state geometries are observed, of which the most common is essentially square-planar at Pt(II), a distorted octahedral at Pt(IV), and some examples of trigonal planar and trigonal bipyramidal as well. The most common ligands are methyl (Me), carbonyl and PX3. The shortest Pt-Pt bond distance is 245.1(1) pm. The mean Pt-Pt bond distance increases in the order: 261.1 pm [Pt(2.5)-Pt(2.5)]<261.3 pm [Pt(III)-Pt(III)]<262.4 pm [Pt(I)-Pt(I)]<270.3 pm [Ot(II)-Pt(II)]<277.2 pm [Pt(0)-Pt(0)]<282.6 pm [Pt(II)-Pt(II)]. The Pt…Pt no-bonding distances are: Pt(II)…Pt(II), 3.008–17.959 pm; Pt(IV)…Pt(IV), 327.5–768.0 pm; Pt(II)-Pt(0), 378.6 pm and Pt(II)…Pt(IV), 389 pm. There are several relationships pointed out between the Pt-Pt distances, Pt-X-Pt bridge angles and covalent radii of coordinated atoms. Several examples contain two crystallographically independent molecules within the same crystal, differing mostly by degree of distortion, which are examples of distortion isomerism.

Platinum organometallic compounds: classification and analysis of crystallographic and structural data. Monomeric Pt compounds with PtC2AB, PtA2BC and PtABCD compositions

2012 ◽  
Vol 32 (2-4) ◽  
pp. 111-180 ◽  
Author(s):  
Milan Melnik ◽  
Ondrej Sprusansky ◽  
Clive Eduard Holloway ◽  
Peter Mikus
Keyword(s):  
Organometallic Compounds ◽  
Structural Data ◽  
Trans Effect ◽  
Square Planar ◽  
Wide Variability ◽  
Cis And Trans ◽  
Planar Environment

AbstractThis review covers almost 350 four-coordinated monomeric organoplatinum complexes with PtC2AB, PtA2BC and PtABCD compositions, and there is wide variability of chromophores. The most common ligands in addition to the C donor are PPh3 and chlorine. Platinum(II) is found only in a square-planar environment involving cis- as well as trans-configurations with a different degree of distortion, especially when bi- or terdentate ligands are present. The trans-effect decreases in the order of the atoms in which the effect dominates, H>C>P>Si>S. There are at least two types of isomerism, cis-trans and distortion. The data strongly suggest that distortion isomerism is, for platinum chemistry, more common than cis- and trans-isomerism.

Stereochemistry of heterobinuclear Pt-M complexes

2017 ◽  
Vol 37 (3-4) ◽  
pp. 131-146 ◽  
Author(s):  
Milan Melnik ◽  
Peter Mikus
Keyword(s):  
Structural Parameters ◽  
The Other ◽  
Oxidation States ◽  
Central Metal ◽  
Metal Atoms ◽  
Square Planar ◽  
Coordination Spheres

AbstractIn this review, the structural parameters of almost 30 isomers of heterobinuclear Pt-M (M=Sn, Tl, Cu, Ag, Ti, W, Cr, Fe, Co, Ni, Mn, Pd, or Rh) complexes are summarized and analyzed. There are three types of isomers: distortion (by far the prevailing type), polymerization, and mixed isomers. On the basis of Pt-M distance, there are two groups of complexes: one in which the Pt-M bond distances are <3.0 Å (M=Sn, Tl, W, Cr, Mn, Ni, or Pd) and the other one in which the Pt-M separations are >3.0 Å (M=Cu, Ag, Ti, W, Fe, Co, or Rh). Platinum atoms exist in two oxidation states: +2 and +4. The former by far prevails with a square-planar arrangement with varying degrees of distortion. The Pt(IV) atoms are six-coordinated. The inner coordination spheres about M atoms range from two-coordinated (AgNCl) to sandwiched (FeC10). There is wide variety of donor atoms (ligands) (H, OL, NL, CL, BL, Cl, SL, PL, Br, or I) that build up the respective inner coordination spheres about central metal atoms.

Platinum organometallic compounds: classification and analysis of crystallographic and structural data. Part I. Monomeric Pt(0) and partly of Pt(II) with PtC4, PtA3B and PtC2A2 chromophores

2012 ◽  
Vol 32 (1) ◽  
pp. 23-79 ◽  
Author(s):  
Milan Melnik ◽  
Clive E. Holloway
Keyword(s):  
Organometallic Compounds ◽  
Structural Data ◽  
Donor Ligands ◽  
Bond Angles ◽  
Square Planar ◽  
Ligand Bond

AbstractThis review covers over 110 monomeric Pt(0) organometallics and 220 monomeric Pt(II) organometallics. The predominant geometry for Pt(0) is square planar, with some examples of two-, five-, and six-coordinated. The monomeric Pt(II) organometallics in the review covers only those with the chromophores PtC4, PtA3B and PtC2A2. The most common ligand, besides C donor ligands, which are of a wide variety, is PPh3. At least two types of isomerism occur in the platinum organometallics analysed in this review: cis-trans and distortion. Relations between Pt-ligand bond distances, bond angles and transeffect are discussed regarding steric and electronic influence.

scholarly journals Analysis of crystallographic and structural data of polymeric FeM (M = transition metals, lanthanides) complexes

2011 ◽  
Vol 9 (5) ◽  
pp. 776-789 ◽  
Author(s):  
Milan Melnik ◽  
Ján Garaj
Keyword(s):  
Transition Metals ◽  
Structural Data ◽  
Oxidation States ◽  
Green Colour ◽  
Lanthanide Elements ◽  
Polymeric Chains ◽  
Rhombohedral Crystal ◽  
Lanthanides Complexes ◽  
Coordination Spheres

AbstractThis review covers crystallographic and structural data for almost fifty polymeric FeM complexes (M = transition Cu, Ag, Au, Mo, W, Mn, Co, Ni and Pt and lanthanide elements Sm, Er and Yb) where iron is involved in polymeric chains. The complexes are for the most part yellow or black, but there are complexes of brown, orange, red, purple, blue and green colour. The complexes crystallized in the monoclinic (by far prevails), triclinic, tetragonal, orthorhombic, trigonal, hexagonal and rhombohedral crystal classes. The iron atoms are found in oxidation states 0, +2 and +3, of which +3 by far prevails. The inner coordination spheres about the Fe(0) atom are tetrahedral (FeC4) or sandwiched (FeC10), Fe(II) atoms are six-coordinated, and Fe(III) are six or even seven-coordinated. The inner coordination about M atoms range from four- through six- to eight-coordinated. The shortest Fe-Fe, Fe-M (transition) and Fe-M (lanthanide) and M-M separations are: 8.08 Å, 3.033 Å for Fe-Cu, 3.010 Å for Fe-Yb and 2.505 Å for Mo-Mo.

Platinum organometallic complexes: classification and analysis of crystallographic and structural data of tri- and oligomeric complexes

2014 ◽  
Vol 34 (4) ◽  
pp. 247-279
Author(s):  
Milan Melník ◽  
Peter Mikuš ◽  
Clive E. Holloway
Keyword(s):  
Bond Distance ◽  
Structural Data ◽  
Coordination Complexes ◽  
Organometallic Complexes ◽  
Oxidation States ◽  
Structural Isomers ◽  
Square Planar ◽  
Distorted Octahedral ◽  
The Mean

AbstractThis review covers almost 100 organoplatinum complexes: trimers (40 examples), tetramers (40 examples), pentamers (4 examples), hexamers (5 examples), nona- and oligomers (8 examples). Platinum is predominantly found in the oxidation states +2 and +4. A number of coordination geometries are observed, the most common being essentially square planar, especially with Pt(II), and distorted octahedral, especially with Pt(IV). The most common ligands are methyl, carbonyl, PX3 and bis(diphenylphosphine)methane. Relationships between the Pt-Pt distances, Pt-X-Pt bridge angles, Pt-L bond distances and covalent radii of coordinated atoms are discussed. The mean Pt-Pt bond distance elongates in the order of nuclearity: 269.0 pm (trimers)<270.5 pm (tetramers)<271.5 pm (dimers)<278.0 pm (oligomers). A comprehensive brief discussion on over 1600 organoplatinum complexes and over 2500 platinum coordination complexes is given. These complexes prefer to crystallize in monoclinic (53%) and triclinic (27%) crystal classes. About l0% of these 4100 plus complexes exist as isomers. It is observed that these isomers are more often stereoisomers than structural isomers and that distortion isomerism is surprisingly more common than the better known cis-trans isomerism, especially in the chemistry of Pt(II) complexes.

Bindungslängen-Bindungsstärken-Beziehungen für Oxide von 4p-, 5p- und 6p-Elementen

1993 ◽  
Vol 204 (1) ◽  
Author(s):  
Stanislav Chladek ◽  
Martin Trömel
Keyword(s):  
Bond Strength ◽  
Bond Length ◽  
Structural Data ◽  
Oxidation States

AbstractBond-length-bond-strength relationships which are valid for different oxidation states of the elements have been established for oxides of As, Se, Br, Pb and Bi. According to new structural data, such relationships of single oxidation states in oxides of Ga(III), Ge(IV), In(III), Tl(I) and Tl(III) have been recalculated as well as those for oxides of Sn, Sb, Te, and I.

scholarly journals Crystallographic and structural characterization of heterometallic platinum compounds. Part II. Heterobinuclear Pt compounds with Pt⋯M (M = transition or lantanide metal) > 3.0 Å

2012 ◽  
Vol 10 (6) ◽  
pp. 1709-1759 ◽  
Author(s):  
Milan Melnik ◽  
Ondrej Sprusansky ◽  
Clive Holloway
Keyword(s):  
Transition Metal ◽  
Chlorine Atom ◽  
Structural Characterization ◽  
Platinum Compounds ◽  
Factors Affecting ◽  
Bond Lengths ◽  
Trigonal Bipyramidal ◽  
Square Planar ◽  
Independent Molecules

AbstractThis review covers almost two hundred and twenty heterobinuclear platinum compounds in which Pt⋯M separation is over 3.0 Å. The M is a transition metal (Cu, Ag, Au, Ti, V, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni and Pd). There is an example of a lanthanide, Yb and a actinide, U. The Pt atom has oxidation numbers 0, +2 and +4. The Pt coordination geometries include trigonal planar Pt(0); square planar Pt(II); trigonal bipyramidal, and pseudo octahedral Pt(IV), with the most frequent being square planar. The most common ligands for Pt are P and C donor atoms, as well as a chlorine atom. The Pt — Ag distance of 3.002(1) Å is the shortest found in this series. There are examples which contain two crystallographically independent molecules, which differ mostly by degree of distortion and even one unique example, which contains eight such molecules. These are examples of distortion isomerism. Factors affecting bond lengths and angles are discussed and some ambiguities in coordination polyhedral are outlined.

Binuclear metal chelate complexes of anthraquinones having a MO4 chromophore. Part 1. Quinizarin

1987 ◽  
Vol 65 (7) ◽  
pp. 1485-1490 ◽  
Author(s):  
M. N. Bakola-Christianopoulou ◽  
P. D. Akrivos ◽  
M. Baumgarten
Keyword(s):  
Metal Ions ◽  
Magnetic Measurements ◽  
Metal Chelate ◽  
Transition Elements ◽  
Chelate Complexes ◽  
Cobalt Nickel ◽  
Oxygen Donor ◽  
Nickel Copper ◽  
Square Planar ◽  
Coordination Spheres

Homobinuclear metal chelate complexes having 1,4-dihydroxy-9,10-anthracenedione (quinizarin) as a bridging unit have been prepared with four bivalent first row transition elements, namely cobalt, nickel, copper, and zinc. The coordination spheres of the metal ions consist of two nearly equivalent six-membered rings with oxygen donor atoms derived from the quinizarin and the terminal ligands which are either β-diketones or salicylic aldehyde. TG, spectroscopic (ir, uv–vis, epr), and magnetic measurements have been applied to an investigation of the geometry adopted by the MO4 chromophores. The results are consistent with varying degrees of distortion from the ideal square planar toward a tetrahedral arrangement around the metal ions, closely related to the specific metal center involved.

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