Charge - Transfer Complexes of Metal Dithiolenes XXIV: Ion Pairs of the Tetrakis(dimethylamino)ethene Dication with Dithiolene Metalate Dianions

Lemke, Matthias; Knoch, Falk; Kisch, Horst

doi:10.1515/znb-1997-0113

Cited by 3 publications

(1 citation statement)

References 9 publications

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“…In several other derivatives, [Pt(η 2 -S 4 ) 2 ] (-2anion) 22 , [Pt(η 2 -dtox) 2 ](-2anion) [23][24][25][26][27] , [Pt(η 2eebt) 2 ] 28 , [Pt(η 2 -mnt) 2 ](-2anion) [29][30][31][32][33][34][35] , [Pt(η 2 -dmit) 2 ] (-2anion) 36,37 , [Pt(η 2 -dtsq) 2 ](-2anion) 38 [47][48][49] and [Pt(η 2 -odtc) 2 ](+2cation) 50 , two identical bidentate (S,S) ligands in each case form two five-membered rings about the Pt(II) atoms, representing the most common situation for PtS 4 chromophores. The Pt-S bond distances range from 2.24 to 2.32 Å with a mean value of 2.29 Å.…”

Section: Pts 4 Derivativesmentioning

confidence: 99%

THIO-LIGANDS in MONOMERIC Pt(II) COMPLEXES – STRUCTURAL ASPECTS

2017

AJCR

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This review includes over three hundred derivatives in which each Pt(II) atom is in a distorted square planar environment with inner coordination spheres of PtS4, PtS3X, PtS2X2, PtSX3, PtS2XY, PtSX2Y and PtSXYZ. There is a wide variety of mono-, bi-, ter-, and tetra-dentate ligands, all incorporating both homoand hetero-dentate varieties. The most common ligands are dimethylsulphoxide and triphenylphosphine. The chelating ligands create a wide variety of metallocyclic rings, where the effects of both steric and electronic factors are observed. Examples of cis-and trans-isomerism exists in these derivatives as well as distortion isomerism, which is much more common. Ligands exerting the trans-effect in these Pt(II) complexes are stronger in the order: OL, NL < Cl < Br < I < SL < H ~ AsL ~ PL ~ CN. Several relationships between the structural parameters were found and are discussed. The complexes crystallized in five crystal classes: hexagonal (0.4%) < tetragonal (1.5%) < orthorhombic (13.8%) < triclinic (23.7%) < monoclinic (60.7%).

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Section: Pts 4 Derivativesmentioning

confidence: 99%

THIO-LIGANDS in MONOMERIC Pt(II) COMPLEXES – STRUCTURAL ASPECTS

2017

AJCR

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Exploration of a new building block for the construction of cyano-bridged solvatomagnetic assemblies: [Ni(cyclam)]³⁺

et al. 2016

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Two 1D CN-bridged coordination polymers based on the cyclam (cyclam = 1,4,8,11tetraazacyclotetradecane) complex of nickel in an unusual oxidation state III have been characterised in terms of structure and solvatomagnetic properties. The {[NiĲcyclam)]ĳCrĲCN) 6 ]•6H 2 O} n (1) and {[Ni(cyclam)][Fe(CN) 6 ]•6H 2 O} n (2) chains are isostructural and crystallise in space group C2/m. They undergo reversible partial dehydration at 40 °C to {[Ni(cyclam)][Cr(CN) 6 ]•3H 2 O} n (1d) and {[Ni(cyclam)][Fe(CN) 6 ]•3H 2 O} n (2d), accompanied by marked changes in structure and magnetic properties.Strong ferromagnetic exchange interaction J along the chains, together with a much weaker inter-chain interaction, leads to magnetic ordering in the range from 2.4 to 5.8 K. Dehydration of 1 leads to a decrease in J from 32 to 18 K, while dehydration of 2 leads to an increase in J from 6.8 to 14.3 K (interaction Hamiltonian −2JS Ni S M ). The magnetic susceptibility for the Cr III -Ni III 3/2-1/2 spin alternating Heisenberg chain was analysed with the help of quantum Monte Carlo simulations, simultaneously including both intra-and inter-chain interactions for a bunch of chains. The compounds are the first bimetallic CNbridged assemblies containing a magnetically coupled octahedral cationic building block of an LS d 7 configuration.

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Ion Pairs between Maleonitriledithiolato Complex Dianions of Cobalt and Nickel and Macrocyclic Ligand Complex Dications of Nickel(II) — Control of Intrapair Interaction through Ligand Modification

Nowicka¹,

Schmauch²,

Chihara³

et al. 2002

Bulletin of the Chemical Society of Japan

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The ion pairs {[Ni(cyclam)]2+[M(mnt)2]2−} (M = Co, Ni: 1a,b), {[Ni(tmc)]2+[M(mnt)2]2−} (M = Co, Ni: 2a,b) and the solvent complexes {[Ni(cyclam)(dmso)2]2+[M(mnt)2]2−} (M = Co, Ni, mnt2− = maleonitriledithiolato = (Z)1,2-dicyano-1,2-ethylenedithiolato, cyclam = 1,4,8,11-tetraazacyclotetradecane, tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) were isolated and structurally characterised. The nature of the macrocyclic ligand and the presence of coordinating solvents determine whether the dication is present as a tetra-, penta- or hexacoordinated complex. In 1a the tetracoordinated dications and dianions are arranged in a mixed stack structure; the absences of any short contacts and of a mutual ion pair charge transfer band indicate the absence of charge transfer interaction. The highly puckered cyclam ligand will prevent a close approach of the planar bis(maleonitriledithiolato)cobaltate(II). When cyclam is replaced by its tetramethyl derivative tmc, a strong coordinative interaction is introduced as indicated by the structure of 2a. One dianion coordinates to two dications through two trans-cyano groups. The resulting trinuclear dications {[Ni(tmc)][Co(mnt)2][Ni(tmc)]}2+ form segregated columns separated by the non-interacting, remaining dianion. Crystallisation in the presence of a coordinating solvent like dimethyl sulfoxide (dmso) leads to the ion pairs {[Ni(cyclam)(dmso)2]2+[M(mnt)2]2−}containing hexacoordinated dications. Magnetic susceptibility measurements at room temperature are in accord with the observed structures. While 1b is diamagnetic, 1a, 2a, 2b, and the two solvent complexes exhibit values characteristic of the isolated ions, in agreement with the absence of any electronic interaction between dication and dianion within the ion pair. Temperature- dependent measurements down to 1.7 K indicate that a weak antiferromagnetic interaction is present in 2a.

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Charge - Transfer Complexes of Metal Dithiolenes XXIV: Ion Pairs of the Tetrakis(dimethylamino)ethene Dication with Dithiolene Metalate Dianions

Cited by 3 publications

References 9 publications

THIO-LIGANDS in MONOMERIC Pt(II) COMPLEXES – STRUCTURAL ASPECTS

THIO-LIGANDS in MONOMERIC Pt(II) COMPLEXES – STRUCTURAL ASPECTS

Exploration of a new building block for the construction of cyano-bridged solvatomagnetic assemblies: [Ni(cyclam)]³⁺

Ion Pairs between Maleonitriledithiolato Complex Dianions of Cobalt and Nickel and Macrocyclic Ligand Complex Dications of Nickel(II) — Control of Intrapair Interaction through Ligand Modification

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Charge - Transfer Complexes of Metal Dithiolenes XXIV: Ion Pairs of the Tetrakis(dimethylamino)ethene Dication with Dithiolene Metalate Dianions

Cited by 3 publications

References 9 publications

THIO-LIGANDS in MONOMERIC Pt(II) COMPLEXES – STRUCTURAL ASPECTS

THIO-LIGANDS in MONOMERIC Pt(II) COMPLEXES – STRUCTURAL ASPECTS

Exploration of a new building block for the construction of cyano-bridged solvatomagnetic assemblies: [Ni(cyclam)]3+

Ion Pairs between Maleonitriledithiolato Complex Dianions of Cobalt and Nickel and Macrocyclic Ligand Complex Dications of Nickel(II) — Control of Intrapair Interaction through Ligand Modification

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Exploration of a new building block for the construction of cyano-bridged solvatomagnetic assemblies: [Ni(cyclam)]³⁺