Complexes Derived from Strong Field Ligands. XV. The Formation of Trinuclear Complexes by Coördination of Tris(β-mercaptoethylamine)-cobalt(III) to Metal Ions

Busch, Daryle H.; Jicha, Donald C.

doi:10.1021/ic50004a036

Cited by 96 publications

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“…In 1962, Busch described the cobalt(III) complex [( 2 ) 3 Co] of 2‐amino‐thioethane 2 in which the three ligands adopt a syn ‐orientation and are able to additionally coordinate through sulfur to other metals. Thus, the subsequent addition of cobalt(III) or nickel(II) salts resulted in the dimerization of the monomeric trisligand complex leading to a hierarchically formed trinuclear coordination compound [{( 2 ) 3 Co} 2 M] n + . The obtained complex showed some features comparable to helicates without having three distinct ligands wrapping the metal centers.…”

Section: Hierarchical Helicatessupporting

confidence: 86%

“…In 1962, Busch described the cobalt(III) complex[ ( 2) 3 Co] of 2amino-thioethane 2 in whicht he three ligandsa dopt a syn-orientation and are able to additionally coordinate through sulfur to other metals.T hus, the subsequenta ddition of cobalt(III)o r nickel(II) salts resulted in the dimerizationo ft he monomeric trisligandc omplex leadingt oah ierarchically formed trinuclear coordination compound [{(2) 3 Co} 2 M] n + . [5] The obtained complex showed some features comparable to helicates without having three distinct ligands wrapping the metal centers. In 1987, Konno et al described the reactiono ft he mononuclear cobalt(III) complex [(2) 3 Co] with silver(I)i ons resulting in a triple-bridged biscobalt complex with three ligand strands wrapping the two cobalt centers [{(2) 3 Co} 2 Ag 3 ] 3 + .T his compound is ah elicate having three non-covalently linked ligands containing bridging silver moieties (Scheme 1).…”

Section: Hierarchical Helicatesmentioning

confidence: 90%

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From Hierarchical Helicates to Functional Supramolecular Devices

Albrecht

Chen

Craen

2019

Chemistry A European J

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Catechol ligands with aldehyde, ketone or ester groups attached in 3‐position form, in the presence of titanium(IV) triscatecholate, titanium(IV) complexes. If lithium cations are the counterions, they can bind in a successive step to the salicylate units of the complex and form a dimeric triple‐lithium‐bridged dinuclear helicate. In solution, the dimer is in equilibrium with the monomer and the thermodynamics of the dimerization can be easily evaluated. Thus, the hierarchically assembled titanium(IV) helicates represent a lithium‐dependent molecular switch. The investigation of different derivatives of the complex allows for an estimation of the influence of side chain functionalities on the energetics of the dimerization. Thus, the hierarchically assembled helicates can be used as a kind of molecular balance to determine weak interaction energies (solvophobic effects and even dispersive effects). In addition, tethering of two ligands leads to “classical” helicates. Removal or addition of lithium cations allows for a reversible switching between a compressed and expanded state, which in the case of chiral ligands can be even performed stereospecifically.

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Section: Hierarchical Helicatessupporting

confidence: 86%

Section: Hierarchical Helicatesmentioning

confidence: 90%

From Hierarchical Helicates to Functional Supramolecular Devices

Albrecht

Chen

Craen

2019

Chemistry A European J

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“…Method A. To a solution containing 1.00 g (2.06 mmol) of [RuCl 2 (DMSO) 4 ] 12 in 200 mL of ethanol was added 0.48 g (6.22 mmol) of Haet. The mixture was refluxed in an oil bath for 3 h under a nitrogen atmosphere.…”

Section: Methodsmentioning

confidence: 99%

Linear-Type S-Bridged Triruthenium Complexes with Aliphatic Aminothiolate Ligands: Synthesis, Characterization, and Properties

et al. 2005

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Treatment of [RuCl(2)(DMSO)(4)] with 2-aminoethanethiol (Haet) in ethanol gave a dicationic triruthenium complex, [Ru[Ru(aet)(3)](2)]Cl(2) ([1]Cl(2)). Complex [1]Cl(2) was also obtained by treatment of RuCl(3).nH(2)O with excess Haet in water. When [1](2+) was chromatographed on a cation-exchange column of SP-Sephadex C-25, meso (DeltaLambda) and racemic (DeltaDelta/LambdaLambda) isomers of the corresponding tricationic complex, [Ru[Ru(aet)(3)](2)](3+) ([2](3+)), were eluted with aqueous NaNO(3). The racemic isomer of [2](3+) was optically resolved into DeltaDelta and LambdaLambda isomers by using [Sb(2)(R,R-tartrato)(2)](2-) as a resolving agent. The molecular structures of DeltaLambda- and DeltaDelta/LambdaLambda-[2](NO(3))(3) were determined by X-ray crystallography. In these complexes, the central Ru atom is coordinated by six thiolato groups from two terminal fac-(S)-[Ru(aet)(3)] units in an octahedral geometry, forming a linear-type S-bridged triruthenium structure. The spectroelectrochemical studies on the electronic absorption and CD spectra, together with the electrochemical studies, demonstrated that [1](2+) and [2](3+) are interconvertible with each other through a one-electron redox process, retaining the chirality of the triruthenium structure. Their electronic structures were investigated on the basis of EPR and magnetic susceptibility measurements, which indicated that [1](2+) and [2](3+) have spin ground states of S(t) = 0 and S(t) = 1/2, respectively. The corresponding L-cysteinato complex, [Ru[Ru(L-cys-N,S)(3)](2)](3-), which was formed from RuCl(3).nH(2)O and excess L-cysteine (L-H(2)cys) in water followed by air oxidation, is also presented.

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“…In addition, the ability of such ML 3 complexes to act as metalloligands to a central metal and form linear trinuclear species of the form [M′(ML 3 ) 2 ] n+ has been known since the 1960's [11, 12]. There are a number of structurally characterized examples of such species with L = aet (and closely related L = cysteinate) [13-29], however there are no structurally characterized examples of such complexes with L = abt.…”

Section: Introductionmentioning

confidence: 99%

A linear S-bridged trinuclear cobalt(III) complex with 2-aminobenzenethiol: synthesis, crystal structure, and spectroscopic characterization

Panja

Moore

Eichhorn

2013

Journal of Coordination Chemistry

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Treatment of cobalt(II) perchlorate hexahydrate with 2 molar equiv. of 2-aminobenzenethiol (Habt) in acetonitrile afforded a tricationic tricobalt complex, [Co{Co(abt)3}2](ClO4)3·2CH3CN, by aerial oxidation. The molecular structure of the meso (ΔΛ) form of the complex was determined by X-ray crystallography. In the complex cation, the central Co is coordinated by six thiolate groups from two terminal fac(S)-[Co(abt)3] units in an octahedral geometry, forming a linear S-bridged tricobalt structure.

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Complexes Derived from Strong Field Ligands. XV. The Formation of Trinuclear Complexes by Coördination of Tris(β-mercaptoethylamine)-cobalt(III) to Metal Ions

Cited by 96 publications

References 0 publications

From Hierarchical Helicates to Functional Supramolecular Devices

From Hierarchical Helicates to Functional Supramolecular Devices

Linear-Type S-Bridged Triruthenium Complexes with Aliphatic Aminothiolate Ligands: Synthesis, Characterization, and Properties

A linear S-bridged trinuclear cobalt(III) complex with 2-aminobenzenethiol: synthesis, crystal structure, and spectroscopic characterization

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