Metal Complexes Based on Tetrathiafulvalene‐Fused π‐Extended Schiff Base Ligands – Syntheses, Characterization, and Properties

Qin, Jie; Qian, Chenxi; Zhou, Nan; Zhu, Rui; Li, Yi‐Zhi; Zuo, Jing‐Lin; You, Xiao‐Zeng

doi:10.1002/ejic.201101022

Cited by 24 publications

(3 citation statements)

References 77 publications

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“…The bonds C16–C23 (1.40 Å) and C19–C21 (1.34 Å) also show double bond character and thus support the assumption that ligand 3 is neutrally charged . Planarity prevails for the TTF unit in 3 as a whole, as has been previously found in several TTF derivatives in the solid state. − …”

Section: Resultsmentioning

confidence: 99%

Iron(II) Spin Crossover Complexes Based on a Redox Active Equatorial Schiff-Base-Like Ligand

et al. 2020

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In this work, two iron(II) coordination compounds with a N 2 O 2 coordinating Schiff base-like ligand bearing a redox active tetrathiafulvalene (TTF) unit and pyridine or trans-1,2-bis(4-pyridylethylene) as an axial ligand are synthesized. Crystals suitable for single X-ray structure analysis were obtained for the new ligand. The complexes were characterized by magnetic susceptibility measurements, T-dependent UV−vis spectroscopy, and cyclic voltammetry. Both complexes display spin transition behavior below room temperature with T 1/2 values of 146 and 156 K. The mononuclear iron(II) complex [Fe TTF L(py) 2 ] is relatively stable up to 400 K compared to similar complexes, showing no loss of axial ligands upon heating. Temperature dependent Mossbauer spectroscopy was conducted for the coordination polymer {[Fe TTF L(bpee)]} n to get more information regarding the origin of the stepwise spin crossover (SCO) behavior observed in the magnetic measurements. The change of the spin state is accompanied by a change of the optical properties, which can be monitored by VT−UV−vis spectroscopy for the mononuclear complex and has been analyzed in theoretical studies. The redox behavior of the iron(II) complexes reveals three reversible redox steps which are located at the iron center and at the TTF unit of the ligand. Oxidation of the TTF unit induces characteristic changes in the UV−vis spectrum that can be followed by spectroelectrochemical UV−vis spectroscopy. Addressing the potential of the ironcentered redox process results in similar changes in the UV−vis spectrum, which indicates an electronic coupling of the redox active unit with the metal center under certain circumstances.

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Section: Resultsmentioning

confidence: 99%

Iron(II) Spin Crossover Complexes Based on a Redox Active Equatorial Schiff-Base-Like Ligand

et al. 2020

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“…It is also worth mentioning that the carbenium ion can be weighed in open air and can be conveniently stored in closed vials at room temperature for months without any appreciable decomposition. This commercially available carbenium ion displays a rich chemistry in material science, where it is used as precursor of fulvalenes . The utility and versatility of this carbenium ion is fully realized when the simple elimination of the sulfur group is carried out with Ni‐Raney.…”

Section: Discussionmentioning

confidence: 99%

A Practical and Stereoselective Organocatalytic Alkylation of Aldehydes with Benzodithiolylium Tetrafluoroborate

et al. 2014

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Recently, the direct substitution of allylic, benzylic, and tertiary alcohols has been achieved via SN 1-type reactions with catalytic amounts of Brønsted or Lewis acids. When a new stereogenic center is formed most of these transformations produce the desired product as a racemate, as these reactions proceed through carbenium ions. The arsenal of activation modes available in organocatalysis can be used to set up suitable reaction conditions in which chiral nucleophiles (enamine catalysis) or chiral electrophiles (iminium catalysis, chiral counterion catalysis) can easily be generated. Recently, we have used stabilized carbenium ions, directly available or obtained from the corresponding alcohols, in new organocatalytic stereoselective SN 1-type reactions. The commercially available carbenium ion benzodithiolylium tetrafluoroborate can be used for the straightforward organocatalytic stereoselective alkylation of aldehydes. In this account we will illustrate the application of this methodology in the total synthesis of natural products and the preparation of valuable starting materials.

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“…In order to address this challenge, considerable effort has been devoted in associating the TTF moiety with an inorganic component and various organic mono-or polydentate ligands, and their corresponding electroactive metal complexes have therefore been reported [6]. For example, metal complexes of phosphines [7][8][9][10][11][12], dithiolates [13], acetylacetonates [14], pyridines [15][16][17], bipyridines [18,19] and more recently of Schiff bases [20][21][22] have been synthesized. Pyridine based Schiff bases ligands such as 2,6-bis(imino)pyridyl, with chelating abilities, form stable complexes, with various transition metals, which have been extensively used as catalysts for olefin polymerization [23,24].…”

Section: Open Accessmentioning

confidence: 99%

Electroactive Bisiminopyridine Ligands: Synthesis and Complexation Studies

et al. 2012

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Abstract:The condensation reaction of (4-(6,7-dimethyldithio-tetrathiafulvalene)-aniline) with 2,6-diformylpyridine afforded an electroactive Schiff base (N,N,N) pincer (3). This pincer was reacted with Zn(II) cation to yield the corresponding Zinc chloride complex (4). The crystal structure of the newly prepared electroactive zinc complex reveals that the tetrathiafulvalene (TTF) is neutral and the zinc cation is pentacoordinated. The two chlorines are involved in a set of hydrogen bonds giving rise to a 2D supramolecular grid arrangement. The electronic absorption properties and the electrochemical behavior have been elucidated. These two compounds are promising for the construction of crystalline radical cation salts.

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Metal Complexes Based on Tetrathiafulvalene‐Fused π‐Extended Schiff Base Ligands – Syntheses, Characterization, and Properties

Abstract: Four metal complexes based on these Schiff base pyridineII , L = L 2 , 6; hfac = hexafluoroacetylacetonate) and

Cited by 24 publications

References 77 publications

Iron(II) Spin Crossover Complexes Based on a Redox Active Equatorial Schiff-Base-Like Ligand

Iron(II) Spin Crossover Complexes Based on a Redox Active Equatorial Schiff-Base-Like Ligand

A Practical and Stereoselective Organocatalytic Alkylation of Aldehydes with Benzodithiolylium Tetrafluoroborate

Electroactive Bisiminopyridine Ligands: Synthesis and Complexation Studies

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