X-Ray crystal structure of tetra-acetatobis(tetrathiafulvalene)dirhodium(II) and the properties of its iodine-doped complex

Matsubayashi, Gen‐etsu; Yokoyama, Kenji; Tanaka, Toshio

doi:10.1039/dt9880003059

Cited by 24 publications

(8 citation statements)

References 1 publication

(1 reference statement)

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“…In the IR spectra of 2 , the stretching band of C=C was observed at 1431 cm –1 with a slightly red shift compared to that of 1 at 1439 cm –1 . It is well known that the central C=C stretching of TTF undergoes a large down‐shift in frequency on oxidation (normally more than 50–100 cm –1 ) 28,29. Therefore, the ligand in the CuI complex is in neutral state, which is in agreement with the molecular composition deduced from microanalysis.…”

Section: Resultssupporting

confidence: 79%

Coordination Assembly of TTF Derivatives through CuI Bridges

Yan

Dai

et al. 2005

Eur J Inorg Chem

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The sulfur‐rich ligand C12H12O4S6 (1) and complexes [(C12H12O4S6)CuI]2 (2) and [(C7H6O4S3)CuI]∞ (3) have been synthesized and characterized crystallographically. Molecules of compound 1, a tetrathiafulvalene (TTF) derivative, have a boat‐shaped configuration and are packed discretely within the crystal. Compound 1 coordinates to a rhomboid CuI center forming a dimeric TTF derivative 2. In complex 2 the boat‐shaped configuration of 1 is flattened. Molecules of 2 are packed regularly and compactly in the crystal and are arranged side by side with short S···S contacts, which assemble the molecules into a 1D ribbon structure. This provides evidence that metal coordination or assembly is a useful stratagem for changing the molecular configuration and packing that further influence the intermolecular interactions. Complex 3 has a step‐like polymeric structure formed by copper‐iodine bridges and copper‐sulfur bridges (coordinated thiocarbonyl). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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Section: Resultssupporting

confidence: 79%

Coordination Assembly of TTF Derivatives through CuI Bridges

Yan

Dai

et al. 2005

Eur J Inorg Chem

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“…The Rh-S bond length (2.474 -2.484 Å) is the shortest Rh-S distance reported for a thioether axially coordinated to Rh2(AcO)4 (generally ranging from 2.517 to 2.560 Å). [41][42][43][44] This distance is also 0.1 Å shorter than the refined distance of 2.58 ± 0.02 Å obtained for a Rh2(AcO)4 methionine solution (C1 = 6.45 mM, 1:2 mole ratio) by X-ray absorption spectroscopy. 18 The Rh-Rh distance of 2.404(2) Å is slightly elongated relative to that of the diaqua adduct, [Rh2(AcO)4(H2O)2] (2.3855(5) Å), 45 but within the range for dirhodium(II) tetraacetate complexes axially coordinated to thioether ligands (2.403 -2.413 Å).…”

Section: Formation Of Rh2(aco)4 Adducts With S-methyl-l-cysteinecontrasting

confidence: 50%

Reaction of dirhodium(II) tetraacetate withS-methyl-L-cysteine

Brunskill

Garcia

Jalilehvand

et al. 2019

Journal of Coordination Chemistry

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The reaction of antitumor active dirhodium(II) tetraacetate, Rh2(AcO)4, with S-methyl-L-cysteine (HSMC) was studied at the pH of mixing (= 4.8) in aqueous media at various temperatures under aerobic conditions. The results from UV-vis spectroscopy and electrospray ionization mass spectrometry (ESI-MS) showed that HSMC initially coordinates via its sulfur atom to the axial positions of the paddlewheel framework of the dirhodium(II) complex, and was confirmed by the crystal structure of [Rh2(AcO)4(HSMC)2]. After some time (48 hours at 25 o C), or at elevated temperature (40 •C), Rh-SMC chelate formation causes breakdown of the paddlewheel structure,

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“…The refined mean Rh-S axial distance 2.58 ± 0.02 Å is comparable to the Rh-S axial distances (2.517 – 2.561 Å) in crystalline thioether adducts of dirhodium(II) carboxylates. 46, 56-58…”

Section: Resultsmentioning

confidence: 99%

Methionine Binding to Dirhodium(II) Tetraacetate

et al. 2018

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The reaction between antitumor active dirhodium(II) tetraacetate and DL-methionine (HMet) was followed in aqueous solution and showed initially mixtures of 1:1 and 1:2 adducts [Rh2(AcO)4(HMet)(H2O)] (AcO− = CH3COO−) and [Rh2(AcO)4(HMet)2] formed at room temperature (RT), as evidenced by UV-vis spectroscopy and electrospray ionization mass spectrometry (ESI-MS). Rh K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy confirmed methionine thioether binding to the axial positions of the Rh2(AcO)4 cage structure. With excess HMet at RT stepwise displacement of the acetate groups was observed after some time using ESI-MS. Heating the solution to 40° for 24 h accelerated the substitution reaction leading to stable dirhodium(II) species with two acetate ligands displaced by two methionine groups. The crystal structure of the purple [RhII2(AcO)2(D-Met)(L-Met)]·6H2O compound obtained from the solution revealed tridentate coordination of the methionine ligands to the Rh(II) ions, with the thioether S atoms in equatorial positions. A minor amount of a light orange monomeric [RhIII(Met)2](AcO) complex also formed in the solution was isolated by size exclusion chromatography, and identified by ESI-MS. Crystals of [RhIII(D-Met)(L-Met)]Cl·3H2O were prepared by reacting RhCl3 and DL-HMet. The crystal structure showed tridentate binding of the methionine ligands to the Rh(III) ion in a trans-S,N,O arrangement.

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X-Ray crystal structure of tetra-acetatobis(tetrathiafulvalene)dirhodium(II) and the properties of its iodine-doped complex

Cited by 24 publications

References 1 publication

Coordination Assembly of TTF Derivatives through CuI Bridges

Coordination Assembly of TTF Derivatives through CuI Bridges

Reaction of dirhodium(II) tetraacetate withS-methyl-L-cysteine

Methionine Binding to Dirhodium(II) Tetraacetate

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