Organometallic compounds of furan, thiophene, and their benzannulated derivatives

Sadimenko, Alexander P.

doi:10.1016/s0065-2725(01)78002-6

Cited by 30 publications

(2 citation statements)

References 325 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Thus, different studies related to their biodegradation and catalytic dehydrodesulfuration have been carried out. In this regard, several reviews of various aspects of thiophene coordination and reactivity in transition metal complexes have been reported …”

Section: Introductionmentioning

confidence: 99%

Experimental and Computational Thermochemical Study of 2- and 3-Thiopheneacetic Acid Methyl Esters

Roux

Temprado²,

Notario³

et al. 2007

J. Phys. Chem. A

View full text Add to dashboard Cite

Thiophene-based compounds have widespread use in modern drug design, biodiagnostics, electronic and optoelectronic devices, and conductive polymers. The present study reports an experimental and computational thermochemical study on the relative stabilities of 2- and 3-thiopheneacetic acid methyl esters. The enthalpies of combustion and vaporization were measured by a rotating-bomb combustion calorimeter, Calvet microcalorimetry, and correlation gas chromatography, and the gas-phase enthalpies of formation at T=298.15 K were determined. Standard ab initio molecular orbital calculations at the G3 level were performed, and a theoretical study of the molecular and electronic structure of the compounds studied was carried out. Calculated enthalpies of formation, using atomization and isodesmic reactions are in very good agreement with the experimental results.

show abstract

Section: Introductionmentioning

confidence: 99%

Experimental and Computational Thermochemical Study of 2- and 3-Thiopheneacetic Acid Methyl Esters

Roux

Temprado²,

Notario³

et al. 2007

J. Phys. Chem. A

View full text Add to dashboard Cite

show abstract

“…Thiophenes are very weak sulfur-donor ligands compared to alkyl or aryl-alkyl sulfides. Their aromatic character accounts for several different coordination modes in homogeneous transition metal complexes that include a direct bond between the sulfur atom and the metal (η 1 (S)) or the carbon atoms of the π ring system and the metal (η 2 , η 4 , and η 5 ). ,, The binding geometry of the thiophenes is generally modified by steric and electronic properties of other ligands attached to the metal center . Accurate knowledge of thiophene coordination chemistry and structural details in homogeneous metal complexes has been obtained from spectroscopic, crystallographic, and density functional theory (DFT)-based mechanistic studies. − There are, however, very few similarly detailed studies of binding to metals and metal complexes in heterogenous environments involving solid supports …”

Section: Introductionmentioning

confidence: 99%

In Situ Imaging and Computational Modeling Reveal That Thiophene Complexation with Co(II)porphyrin/Graphite Is Highly Cooperative

et al. 2022

View full text Add to dashboard Cite

Scanning tunneling microscopy (STM) was employed to quantitively investigate in situ binding of 3-phenyl thiophene (PhTh) to Co(II)octaethyl porphyrin (CoOEP) supported on highly ordered pyrolytic graphite (HOPG) in fluid solution. To our knowledge, this is the first single-molecule level study of a complexation reaction between a metalloporphyrin and a sulfur base at the solution/solid interface and one of the few examples of thiophene coordination with a d7 transition metal. Real-time imaging experiments revealed that PhTh binds reversibly to HOPG-supported CoOEP at room temperature. The coordination process increases with increasing PhTh concentration. The nearest-neighbor analysis of STM images indicates that the complexation reaction is cooperative. Because PhTh does not bind to CoOEP in solution, the STM results strongly suggest that the presence of HOPG is crucial to observe ligand binding and cooperativity in this system. Periodic plane-wave density functional theory (DFT) computations corroborate that PhTh has low binding affinity toward CoOEP in solution but predict that the ligand can adsorb to CoOEP/HOPG through coordination with S atoms or interact through noncovalent π–π bonding with the porphyrin chromophore. Three possible structures were considered, and DFT theory was used to calculate binding energies and free energies. In solution and on the HOPG surface both a π–π configuration and a η1(S) configuration have similar computed energies. The η1(S) structure shows the largest stabilization in going from the vapor to adsorbed on HOPG. We also show that statistical analysis of nearest neighbors is more sensitive to cooperative binding than is fitting with the Temkin or Langmuir isotherm. The implication is that isotherm fitting alone is insufficient for identifying cooperative binding on surfaces.

show abstract

N‐Heterocyclic Carbene Stabilized Dicarbondiphosphides: Strong Neutral Four‐Membered Heterocyclic 6π‐Electron Donors

Chen

Liu

et al. 2020

Angewandte Chemie

View full text Add to dashboard Cite

In contrast to cyclic π‐conjugated hydrocarbons, the coordination chemistry of inorganic heterocycles is less developed. Dicarbondiphosphides stabilized by N‐heterocyclic carbenes (NHCs) NHC→C2P2←NHC (1 a,b) (NHC=IPr or SIPr) contain a four‐membered C2P2 ring with an aromatic 6π‐electron configuration. These heterocycles coordinate to a variety of complex fragments with metals from groups 6, 9, and 10, namely [M0(CO)3] (M=Cr, Mo), [CoI(CO)2]+, or [NiIIBr2], through an η4‐coordination mode, leading to complexes 2 a,b, 3 a,b, 5 a,b, and 6 a,b, respectively. These complexes were characterized by X‐ray diffraction methods using single crystals, IR spectroscopy, and DFT calculations. In combination these methods indicate that 1 a,b behave as exceptionally strong 6π‐electron donors.

show abstract

Organometallic compounds of furan, thiophene, and their benzannulated derivatives

Cited by 30 publications

References 325 publications

Experimental and Computational Thermochemical Study of 2- and 3-Thiopheneacetic Acid Methyl Esters

Experimental and Computational Thermochemical Study of 2- and 3-Thiopheneacetic Acid Methyl Esters

In Situ Imaging and Computational Modeling Reveal That Thiophene Complexation with Co(II)porphyrin/Graphite Is Highly Cooperative

N‐Heterocyclic Carbene Stabilized Dicarbondiphosphides: Strong Neutral Four‐Membered Heterocyclic 6π‐Electron Donors

Contact Info

Product

Resources

About