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.

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. 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.

Complexes of hybrid ligands. The synthesis of a thioanisole-substituted fluoro-alcohol and its complexes with Pd2+ and Pt2+; the structure of a palladium(II) complex containing alkoxide, phosphine, thioether, and chloride donors

1987 ◽  
Vol 65 (4) ◽  
pp. 798-803 ◽  
Author(s):  
René T. Boeré ◽  
David E. Esser ◽  
Christopher J. Willis ◽  
Douglas W. Stephan ◽  
Taras W. Obal
Keyword(s):  
Least Squares ◽  
Dihedral Angle ◽  
Chelate Ring ◽  
Monoclinic Space Group ◽  
Structural Determination ◽  
Bond Lengths ◽  
Square Planar ◽  
Planar Molecules ◽  
Hybrid Ligands ◽  
Cis And Trans

The compound 2-thioanisole-1,1,1,3,3,3-hexafluoro-2-propanol, CH3S—C6H4—C(CF3)2OH, HL2, has been prepared, and shown to act (in the ionized form) as a hybrid, chelating, ligand. Neutral bis-complexes M(L2)2 are formed with Pd2+ and Pt2+; the former reacts with PdCl42− to give the Cl-bridged dinuclear complex (L2)Pd(μ-Cl)2Pd(L2), which may in turn be cleaved by PPh3 or PPh2Me to give PdCl(L2)(PR3).A complete structural determination has been made for PdCl(L2)(PPh2Me); C23H20ClF6OPPdS. Crystals are monoclinic, space group P21/n, a = 15.526(5), b = 12.966(9), c = 12.900(8) Å, β = 101.84°, V = 2542(2) Å3, Z = 4. Least-squares refinement on F of 198 variables using 2801 observations converged at R1 = 0.0434, R2 = 0.0559. The complex consists of discrete square-planar molecules with phosphine and alkoxide trans-disposed. Bond lengths are Pd—O, 2.053(3); Pd—P, 2.242(1); Pd—Cl, 2.323(2); Pd—S, 2.252(2) Å. In the six-membered chelate ring, all atoms with the exception of Pd are close to coplanarity; there is a dihedral angle of 127.9° between the O—Pd—S plane and that of the aromatic ring.Multinuclear nmr measurements are used to show that both cis- and trans-forms of complexes PdCl(L2)(PR3) are present in solution, with inversion at coordinated sulfur occurring much more rapidly in the latter.

The Stereospecific Synthesis of Neutral and Cationic Tertiary Phosphine Complexes of Platinum(II)

1974 ◽  
Vol 52 (4) ◽  
pp. 692-695 ◽  
Author(s):  
Keith R. Dixon ◽  
Kenneth C. Moss ◽  
Martin A. R. Smith
Keyword(s):  
Synthetic Methods ◽  
Stereospecific Synthesis ◽  
Tertiary Phosphine ◽  
Phosphine Complexes ◽  
Square Planar ◽  
Cleavage Reactions ◽  
Cis And Trans

Stereospecific synthetic methods for the preparation of complexes of the type cis- and trans[PtClL(PEt3)2]+ and cis-[PtClX(PEt3)2] have been developed. Preparations of complexes where L = py, PPh3, PClPh2, or P(OPh)3 and X = SCN, NO2, NO3, N3, NCO, or Br are described and it is shown that bridge cleavage reactions in square planar platinum(II) complexes occur with retention of stereo chemistry.

scholarly journals Bis(N-nitroso-N-pentylhydroxylaminato-κ2O,O′)copper(II)

2014 ◽  
Vol 70 (4) ◽  
pp. m137-m138
Author(s):  
Ali Sheikh Bostanabad ◽  
Olga Kovalchukova ◽  
Svetlana Strashnova ◽  
Adam Stash ◽  
Igor Zyuzin
Keyword(s):  
Title Compound ◽  
Chelating Ligands ◽  
Wyckoff Position ◽  
Square Planar ◽  
Planar Environment

In the centrosymmetric title compound, [Cu(C5H11N2O2)2], the Cu2+ion, located on an inversion centre (Wyckoff position 2b), is in a square-planar environment, surounded by four O atoms of the N—O groups of twoN-nitroso-N-pentylhydroxylaminate ligands [Cu—O = 1.9042 (17) and 1.9095 (16) Å]. The hydroxylaminate monoanions are bidentate chelating ligands. The Cu2+cations form stacks along [010], with intermolecular Cu...N contacts of 3.146 (2) and 3.653 (2) Å.

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 Applicability of NBO and AIM Topology Analyses to Chemical Bonding in Some Diacetylplatinum(II) Complexes

2019 ◽  
Vol 31 (4) ◽  
pp. 925-937
Author(s):  
Saied M. Soliman ◽  
Mohamed M. Zaid
Keyword(s):  
Critical Points ◽  
Chemical Bonding ◽  
Basis Sets ◽  
Dft Methods ◽  
Geometrical Structures ◽  
Trans Effect ◽  
Hartree Fock ◽  
Square Planar ◽  
Relative Errors ◽  
Back Donation

The geometrical structures of six square-planar diacetylplatinum(II) complexes ([Pt(Ac)2L], L = hydrazine-type ligand) were calculated using six (B3LYP, CAM-B3LYP, B3PW91, M06, M06HF and PBE) DFT methods and one post-Hartree–Fock (MP2) method combined with 6-31G(d,p) basis sets for nonmetal atoms and LANL2DZ for Pt. Using percent relative errors, M06HF and MP2 are best for predicting Pt–N bond distances, but worst for Pt–C bond distances, whereas B3PW91 is best. Pt–N(pyridine) bonds have higher electron density at the bond critical points than Pt–N(hydrazone) bonds, and the former are more covalent than the latter. Further, Pt–C bonds trans to hydrazone moieties are more covalent than Pt–C bonds trans to Pt–N(pyridine) bonds. Pt–C bonds are mainly due to Pt→Ac back donation rather than Ac→Pt donation; σ-bonding is less important in this case, consistent with the high π-acidity and strong trans effect of acetyl groups. In contrast, Pt→N back donation is negligible and Pt–N bonds are mainly due to N→Pt σ-donation, which stabilizes trans Pt–C bonds.

Mechanismus der cis- und trans-Stimulierung der Anionenfluxe durch die Plasmamembran der Pflanzenzelle / Mechanism of Cis- and Trans-Stimulation of Anion Fluxes across the Plasma Membrane of Plant Cells

1970 ◽  
Vol 25 (6) ◽  
pp. 631-636 ◽  
Author(s):  
Josef Weigl
Keyword(s):  
Plasma Membrane ◽  
Permeability Coefficient ◽  
Electrical Potential ◽  
Plant Cells ◽  
Monovalent Cations ◽  
Trans Effect ◽  
Anion Permeation ◽  
Ion Efflux ◽  
Cis And Trans ◽  
Stimulation Of

Trans-stimulation by salts of the passive efflux of Cl⊖ across the plasma membrane of plant cells was established previously. In this paper the trans-effect of salts is compared with the effect of nystatin on ion efflux. It is further shown that the influx of anions is also stimulated by external salts. Influx of Cl⊖ was stimulated by K2SO4 (>~1 mM), influx of SO42⊖ was stimulated by KCl (>~lmM). This suggests that with increasing external salt concentration not only the electrical potential across the plasmalemma is lowered (due to preferential permeability to monovalent cations) but alsoth e permeability (i. e. the permeability coefficient) of the plasmalemma to anions is increased. According to the model proposed for the salt-stimulated decrease in the resistance to passive anion permeation the plasmalemma may be considered a lipid lattice-electrofilter. The nature of the coupling of the counter fluxes is discussed.

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