The Stereochemical activity or non-activity of the ‘Inert’ pair of electrons on lead(II) in relation to its complex stability and structural properties. Some considerations in ligand design

Hancock, Robert D.; Shaikjee, Mooniq; Dobson, Susan M.; Boeyens, Jan C. A.

doi:10.1016/s0020-1693(00)90141-5

Cited by 242 publications

(148 citation statements)

References 26 publications

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“…The four terminal N-coordinated isothiocyanato groups in the [Zn(NCS) 4 ] 2− complex anion form a distorted coordination tetrahedron around Zn3, with bond parameters in the following ranges: Zn3-N: 1.937 (7) • . The S-C average distance of 1.595(2)Å and C-N average distance of 1.165(3)Å are in accordance with the values observed in other thiocyanato-containing metal complexes [18,19]. The shortest Zn···Zn separation is 6.372(2)Å.…”

Section: Description Of the Crystal Structuressupporting

confidence: 86%

Syntheses, structures and properties of a new compound of the type [Zn(4,4′-dmo-2,2′-bpy)2(CH3COO)]2[Zn(SCN)4]·H2O with zinc in two cationic and one anionic complexes

Shirdel

Marandi

Jalilzadeh

et al. 2015

MGC

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A new compound of zinc(II) with the ligand 4,4 -dimethoxy-2,2 -bipyridine(4,4 -dmo-2,2 -bpy), [Zn(4,2bpy) has been obtained as white single crystals by the branched tube method and characterized by elemental analysis, IR and 1 H NMR spectroscopy and by X-ray crystallography. Thermal and electrochemical properties were also studied. The crystal structure consits of two discrete [Zn(4,4 -dmo-2,2 -bpy) 2 (CH 3 COO)] + cations and a [Zn(SCN) 4 ] 2− anion. Zinc(II) cations in the [Zn(4,4 -dmo-2,2 -bpy) 2 (CH 3 COO)] + units have a distorted octahedral surrounding by ZnN 4 O 2 coordinated through four N atoms of 4,4 -dmo-2,2 -bpy and two O atoms of acetate. Zinc(II) in [Zn(SCN) 4 ] 2− has a distorted tetrahedral coordination environment with an ZnN 4 ligated by four N atoms of the terminal thiocyanates. In the solid state, [Zn(4,4 -dmo-2,2 -bpy)(CH 3 COO)] + cations are interconnected by tetrahedral [Zn(NCS) 4 ] 2− units by cooperative C-H•••O, C-H•••S, C-H•••N and π-π stacking interactions resulting in a 2D network structure. Establishment of such networks seems to be aiding the crystallization.

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Section: Description Of the Crystal Structuressupporting

confidence: 86%

Syntheses, structures and properties of a new compound of the type [Zn(4,4′-dmo-2,2′-bpy)2(CH3COO)]2[Zn(SCN)4]·H2O with zinc in two cationic and one anionic complexes

Shirdel

Marandi

Jalilzadeh

et al. 2015

MGC

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“…The arrangement of the oxygen atoms of the (H)salicylate − and (H)phthalate − ligands suggest a gap in the coordination geometry around the metal ions in the both compounds, occupied possibly by a stereoactive lone pair of electrons on the thallium atoms. The observed shortening of the Tl-O bonds on the side of Tl ion opposite to the putative lone pair (Tl1-O2 i = 2.54(6) and Tl1-O4 = 2.743(8)Å compared with Tl1-O3 = 2.93(5) and Tl1-O4 ii = 3.035(9)Å adjacent to the lone pair in 1 and 2, respectively) (Figs 5 and 6) supports the presence of this feature [12].…”

Section: Resultssupporting

confidence: 53%

Thallium(I) Salicylate and Phthalate: Syntheses and Structural Characterization

Askarinejad

Torabi

Morsali

2006

Zeitschrift Für Naturforschung B

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Two new 2D polymers, thallium(I) hydrogensalicylate (1) and hydrogenphthalate (2), have been synthesized and characterized by elemental analysis, IR, 1 H NMR and 13 C NMR spectroscopy. The single-crystal X-ray data show the coordination number of the Tl I ions of compounds 1 and 2 to be four and six with the environment TlO 4 and TlO 6 , respectively. The arrangement of the O atoms suggests a gap in the coordination geometry around the thallium atoms in both compounds, due to a stereo-chemically 'active' electron lone pair of Tl I . There is another interaction between the thallium atom and the carbon atoms of an aromatic ring in compound 1, giving a total hapticity of ten with the environment C 6 O 4 Tl.

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“…Anal. Calcd for C 20 Equilibrium Measurements. The chemicals used in the studies were of the highest analytical grade.…”

Section: ■ Experimental and Computational Sectionmentioning

confidence: 99%

H₄octapa: Highly Stable Complexation of Lanthanide(III) Ions and Copper(II)

et al. 2015

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The acyclic ligand octapa 4− (H 4 octapa = 6,6′-((ethane-1,2-diylbis((carboxymethyl)azanediyl))bis-(methylene))dipicolinic acid) forms stable complexes with the Ln 3+ ions in aqueous solution. The stability constants determined for the complexes with La 3+ , Gd 3+ , and Lu 3+ using relaxometric methods are log K LaL = 20.13(7), log K GdL = 20.23(4), and log K LuL = 20.49(5) (I = 0.15 M NaCl). High stability constants were also determined for the complexes formed with divalent metal ions such as Zn 2+ and Cu 2+ (log K ZnL = 18.91(3) and log K CuL = 22.08 (2)). UV− visible and NMR spectroscopic studies and density functional theory (DFT) calculations point to hexadentate binding of the ligand to Zn 2+ and Cu 2+, the donor atoms of the acetate groups of the ligand remaining uncoordinated. The complexes formed with the Ln 3+ ions are nine-coordinated thanks to the octadentate binding of the ligand and the presence of a coordinated water molecule. The stability constants of the complexes formed with the Ln 3+ ions do not change significantly across the lanthanide series. A DFT investigation shows that this is the result of a subtle balance between the increased binding energies across the 4f period, which contribute to an increasing complex stability, and the parallel increase of the absolute values of the hydration free energies of the Ln 3+ ions. In the case of the [Ln(octapa)(H 2 O)] − complexes the interaction between the amine nitrogen atoms of the ligand and the Ln 3+ ions is weakened along the lanthanide series, and therefore the increased electrostatic interaction does not overcome the increasing hydration energies. A detailed kinetic study of the dissociation of the [Gd(octapa)(H 2 O)]− complex in the presence of Cu 2+ shows that the metal-assisted pathway is the main responsible for complex dissociation at pH 7.4 and physiological [Cu 2+ ] concentration (1 μM).

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The Stereochemical activity or non-activity of the ‘Inert’ pair of electrons on lead(II) in relation to its complex stability and structural properties. Some considerations in ligand design

Cited by 242 publications

References 26 publications

Syntheses, structures and properties of a new compound of the type [Zn(4,4′-dmo-2,2′-bpy)2(CH3COO)]2[Zn(SCN)4]·H2O with zinc in two cationic and one anionic complexes

Syntheses, structures and properties of a new compound of the type [Zn(4,4′-dmo-2,2′-bpy)2(CH3COO)]2[Zn(SCN)4]·H2O with zinc in two cationic and one anionic complexes

Thallium(I) Salicylate and Phthalate: Syntheses and Structural Characterization

H₄octapa: Highly Stable Complexation of Lanthanide(III) Ions and Copper(II)

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The Stereochemical activity or non-activity of the ‘Inert’ pair of electrons on lead(II) in relation to its complex stability and structural properties. Some considerations in ligand design

Cited by 242 publications

References 26 publications

Syntheses, structures and properties of a new compound of the type [Zn(4,4′-dmo-2,2′-bpy)2(CH3COO)]2[Zn(SCN)4]·H2O with zinc in two cationic and one anionic complexes

Syntheses, structures and properties of a new compound of the type [Zn(4,4′-dmo-2,2′-bpy)2(CH3COO)]2[Zn(SCN)4]·H2O with zinc in two cationic and one anionic complexes

Thallium(I) Salicylate and Phthalate: Syntheses and Structural Characterization

H4octapa: Highly Stable Complexation of Lanthanide(III) Ions and Copper(II)

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H₄octapa: Highly Stable Complexation of Lanthanide(III) Ions and Copper(II)