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.

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 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.

scholarly journals Nickel(II) cyclohexylethyl-dithiocarbamate P-donor ligands in the coordination sphere

2004 ◽  
Vol 69 (12) ◽  
pp. 1053-1061 ◽  
Author(s):  
Josef Husárek ◽  
Richard Pstorek ◽  
Michal Malon ◽  
Zedenek Sindalar ◽  
Marek Pavlícek
Keyword(s):  
Thermal Analysis ◽  
Nmr Spectroscopy ◽  
Elemental Analysis ◽  
1H Nmr Spectroscopy ◽  
Chemical Study ◽  
Donor Ligands ◽  
Conductivity Measurements ◽  
Physico Chemical ◽  
Square Planar ◽  
Vis Spectroscopy

A series of new Ni(II) dithiocarbamate compounds of the composition [NiX(cetdtc)(PR3)](X = Cl, Br, I, NCS; cetdtc = cyclohexylethyldithiocarbamate; R = phenyl, n-butyl) has been synthesized. All the isolated complexes have been characterized by elemental analysis, IR and UV/VIS spectroscopy, 31P{1H}-NMR spectroscopy, thermal analysis magnetochemical and conductivity measurements. On the basis of the results of the physico-chemical study, all complexes are diamagnetic, non-electrolytes with a square-planar NiS2PX chromophore.

Crystal structures of 3/4-pyridyl-based thiosemicarbazones and related Cu and Ni coordination compounds

2022 ◽  
Vol 78 (1) ◽  
Author(s):  
Tarlok Singh Lobana ◽  
Mani Kaushal ◽  
Robin Bhatia ◽  
Ritu Bala ◽  
Ray J. Butcher ◽  
...  
Keyword(s):  
Crystal Structures ◽  
Coordination Compounds ◽  
Bond Angle ◽  
Donor Atom ◽  
Neutral Form ◽  
Bond Angles ◽  
Square Planar ◽  
Tetrahedral Bond

In this investigation, the crystal structures of the thio-ligands 3-formylpyridine 4-phenylthiosemicarbazone (C13H12N4S, 1) and 4-benzoylpyridine 4-ethylthiosemicarbazone (C15H16N4S, 2), and of two new coordination compounds, chlorido(3-formylpyridine 4-phenylthiosemicarbazone-κS)bis(triphenylphosphane-κP)copper(I) acetonitrile monosolvate, [CuCl(C13H12N4S)(C18H15P)2]·CH3CN, 3, and bis(3-formylpyridine 4-ethylthiosemicarbazonato-κ2 N 1,S)nickel(II), [Ni(C9H11N4S)2], 4, are reported. In complex 3, the thio-ligand coordinates in a neutral form to the Cu atom through its S-donor atom, and in complex 4, the anionic thio-ligand chelates to the Ni atom through N- and S-donor atoms. The geometry of complex 3 is distorted tetrahedral [bond angles 99.70 (5)–123.23 (5)°], with the P—Cu—P bond angle being the largest, while that of complex 4 is square planar, with trans-S—Ni—S and N—Ni—N bond angles of 180°.

Syntheses, theoretical studies, and crystal structures of [Ni(II)SSRRL](PF6)2 and [Ni(II)SRSRL](Cl)(PF6) that contains anagostic interactions

2020 ◽  
pp. 1-10
Author(s):  
Peyton C. Bainbridge ◽  
Rudy L. Luck ◽  
Nick K. Newberry
Keyword(s):  
Theoretical Calculations ◽  
Structural Data ◽  
Theoretical Studies ◽  
Redox Potentials ◽  
X Ray ◽  
H Nmr ◽  
Irreversible Oxidation ◽  
Square Planar ◽  
Reduced Products ◽  
Reversible Reduction

The syntheses of two square planar nickel complexes containing the condensation and subsequently reduced products obtained by reacting [Ni(en)3](BF4)2 and acetone are reported. The complexes 5,5,7,12,12,14-hexamethyl-1(S),4(S),8(R),11(R)-tetraazacyclotetradecane-nickel(II)[PF6]2 and 5,5,7,12,12,14-hexamethyl-1(S),4(R),8(S),11(R)-tetraazacyclotetradecane-nickel(II)[Cl][PF6] labelled as [Ni(II)SSRRL](PF6)2 and [Ni(II)SRSRL](Cl)(PF6), respectively, were found to have slightly different solubilities that allowed for their purification. The complexes were characterized by FTIR, 1H NMR, and UV–vis spectra. Redox potentials, determined by cyclic voltammetry, established that [Ni(II)SSRRL](PF6)2 exhibits a reversible oxidation (E1/2(ox) = 0.85 V) and reduction (E1/2(red) = −1.59 V), whereas [Ni(II)SRSRL](Cl)(PF6) displays an irreversible oxidation (Epa(ox) = 1.37 V) and reversible reduction (E1/2(red) = −1.62 V) relative to the ferrocene couple at 0.0 V. Single crystal X-ray determinations established that one of the compounds, [Ni(II)SSRRL](PF6)2, contained two [Formula: see text] anions, whereas the other compound, [Ni(II)SRSRL](Cl)(PF6), contained one Cl− and one [Formula: see text] anion. In the solid state, compound [Ni(II)SSRRL](PF6)2 was held together by H-bonds between H atoms on the Ni containing dication and F atoms in the [Formula: see text] anion. Compound [Ni(II)SRSRL](Cl)(PF6) crystallized in the form of dimers held together by interactions between H atoms attached to N atoms on adjacent cations binding to two Cl− anions in the middle with these dimers held together by further H-bonding to interstitial [Formula: see text] anions. Complex [Ni(II)SRSRL](Cl)(PF6) was found to contain anagostic interactions on the bases of NMR (downfield shift in C–H protons) and structural data (2.3 < d(H-Ni) < 2.9 Å), as well as theoretical calculations.

scholarly journals Preparation and Crystal Structure of a Platinum(II) Complex of [CH2N(CH2COOH)CH2CONH2]2, the Hydrolysis Product of an Anti-Tumour Bis(3,5-Dioxopiperazin-1-YL)Alkane

1994 ◽  
Vol 1 (4) ◽  
pp. 321-328 ◽  
Author(s):  
Kevin B. Nolan ◽  
Leo P. Ryan ◽  
Colm J. Campbell ◽  
Patrick McArdle ◽  
Desmond Cunningham ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Hydrolysis Product ◽  
Molecular Structures ◽  
3 Dimensional ◽  
Crystal And Molecular Structures ◽  
Dimensional Network ◽  
Square Planar ◽  
Ligand Bond ◽  
Hydrogen Bonded

The synthesis and crystal and molecular structures of the platinum(II) complex Pt(HL)Cl where H2L is the diacid diamide –[CH2N(CH2COOH)CH2CONH2]2, a hydrolytic metabolite of an antitumour active bis(3,5-dioxopiperazin-1-yl)alkane are reported. The complex is square planar and contains HL− as a tridentate 2N (amino), O (carboxylate) donor. The metal to ligand bond distances are Pt-Cl 2.287(1) Å, Pt-O 2.002 (1) Å, Pt-Ntrans Cl 2.014(1) Å and Pt-Ntrans O 2.073 Å. There is extensive hydrogen bonding, each molecule of Pt(HL)Cl being intermolecularly hydrogen bonded to ten others giving a 3-dimensional network. There is also one intramolecular H-bond.

scholarly journals Structures of Pt(0)P3, Pt(0)P4 and Pt(II)P4 – Distortion isomers

2020 ◽  
Vol 43 (1) ◽  
pp. 111-116
Author(s):  
Milan Melník ◽  
Peter Mikuš
Keyword(s):  
Structural Parameters ◽  
Donor Ligands ◽  
Planar Geometry ◽  
Bidentate Ligands ◽  
Tetrahedral Geometry ◽  
Cooperative Effects ◽  
Square Planar ◽  
Crystal Class ◽  
Planar Geometries

AbstractIn this review are analyzed and classified crystallographic and structural parameters of P(0)P3, Pt(0) P4 and Pt(II)P4 derivatives – distortion isomers. Some of the isomers are differing not only by degree of distortion but also by crystal class. There are three types of organo-phosphines which build up the respective geometry about the platinum atoms. In Pt(0)P3 a distorted trigonal planar geometry is build up by three monodentate PPh3 ligands. In Pt(0)P4 a tetrahedral geometry with various degree of distortion is build up by a pair of homo-bidentate ligands. In Pt(II)P4 isomers a square-planar geometries with various degree of distortion are build up by bidentate-P,P’donor ligands, (except one example of isomers, where a tetradentate is involved). The bidentate-P,P’-donor ligands form: four-(PNP,PCP), five-(PC2P) and six-(PC3P) metallocyclic rings. The tetradentate forms five-(PC2P). There are some cooperative effects between Pt–P bond distances and the metallocyclic rings, and at the same time a distortion of the respective geometry increases.

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