Related Experiment Video
Updated: Aug 18, 2026
Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks (MOFs)
Published on: January 17, 2020
Reactivity of Cubane-Type [(OC)(3)MFe(3)S(4)(SR)(3)](3-) Clusters (M = Mo, W): Interconversion with Cuboidal
James W. Raebiger1, Charles A. Crawford, Jian Zhou
1Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138.
Abstract:
The title clusters, several examples of which have been reported earlier, have been prepared by two different methods and subjected to structural and reactivity studies. The compounds (Et(4)N)(3)[(OC)(3)MFe(3)S(4)(Smes)(3)].MeCN (M = Mo/W) are isomorphous and crystallize in monoclinic space group P2(1)/n with a = 13.412(1)/13.297(1) Å, b = 19.0380(1)/18.9376(3) Å, c = 26.4210(1)/26.2949(1) Å, beta = 97.87(1)/97.549(1) degrees, and Z = 4. The clusters contain long M-S (2.62/2.59 Å) and M-Fe (3.22/3.19 Å) bonds, consistent with the reported structure of [(OC)(3)MoFe(3)S(4)(SEt)(3)](3-) (3). Reaction of [(OC)(3)MoFe(3)S(4)(LS(3))](3-) (7) with CO in the presence of NaPF(6) affords cuboidal [Fe(3)S(4)(LS(3))](3-) (9), also prepared in this laboratory by another route as a synthetic analogue of protein-bound [Fe(3)S(4)](0) clusters. The clusters [Fe(3)S(4)(SR)(3)](3-) (R = mes, Et), of limited stability, were generated by the same reaction. Treatment of 9 with [M(CO)(3)(MeCN)(3)] affords 7 and its M = W analogue. The clusters [(OC)(3)MFe(3)S(4)(SR)(3)](3-) form a four-member electron transfer series in which the 3- cluster can be once reduced (4-) and twice oxidized (2-, 1-) to afford clusters of the indicated charges. The correct assignment of redox couple to potential in the redox series of six clusters is presented, correcting an earlier misassignment of the redox series of 3. Carbonyl stretching frequencies are shown to be sensitive to cluster oxidation state, showing that the M sites and Fe(3)S(4) fragments are electronically coupled despite the long bond distances. (LS(3) = 1,3,5-tris((4,6-dimethyl-3-mercaptophenyl)thio)-2,4,6-tris(p-tolylthio)benzenate(3-); mes = mesityl.)
More Related Videos
06:53Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
04:51Synthesis of Triazole and Tetrazole-Functionalized Zr-Based Metal-Organic Frameworks Through Post-Synthetic Ligand Exchange
Published on: June 23, 2023
Related Concept Videos
02:58Properties of Transition Metals
02:34Structural Isomerism
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can be...
02:42Valence Bond Theory
02:58Crystal Field Theory - Octahedral Complexes
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
02:46Crystal Field Theory - Tetrahedral and Square Planar Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
03:02Colors and Magnetism
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human eye.