Related Experiment Video
Updated: Aug 2, 2026
10:42
Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of Chalcogenidoplumbates(II or IV)
Published on: December 29, 2016
Chalcogen-chalcogen bonds in edge-sharing square-planar d8 complexes. Are they possible?
Gabriel Aullón1, Mohamed Hamidi, Agustí Lledós
1Unitat de Química-Física, Departament de Química, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona, Spain. gabriel.aullon@qi.ub.es
Inorganic Chemistry
|June 8, 2004
Summary
This study reveals that group 10 transition metal complexes can form two distinct X-X bond structures. Metal and ligand properties significantly influence the stability of these short and long bond isomers.
Area of Science:
- Inorganic Chemistry
- Theoretical Chemistry
- Computational Chemistry
Background:
- Complexes with the general formula [M(2)(mu-X)(2)L(4)], where M is a group 10 element and X is a group 16 element, are crucial in various chemical processes.
- These d(8) transition metal complexes exhibit diverse bonding behaviors that are not fully understood.
- Investigating the formation of X-X bonds in these systems is key to understanding their reactivity and stability.
Purpose of the Study:
- To theoretically investigate the formation of X-X bonds in [M(2)(mu-X)(2)L(4)] complexes.
- To analyze the factors influencing the existence of two energy minima (short and long X-X distances).
- To understand the impact of metal, ligand, and bite angle on isomer stability.
Main Methods:
- Density Functional Theory (DFT) calculations were employed.
- Theoretical modeling was used to explore potential energy surfaces.
- Analysis of electronic structure and bonding characteristics.
Main Results:
- The study demonstrates the existence of two stable energy minima for some complexes, corresponding to short and long X-X bond distances.
- The nature of the transition metals (M) and ligands (L) strongly affects the relative stability of these two isomers.
- The bite angle of chelating ligands and the donor atom type also play a significant role in isomer stability.
Conclusions:
- The formation of X-X bonds in these d(8) transition metal complexes is highly sensitive to the electronic and steric properties of the metal and ligands.
- Two distinct structural motifs with different X-X bond lengths can coexist, offering opportunities for tailored synthesis and applications.
- Further theoretical and experimental studies are warranted to fully elucidate the bonding nuances in these important inorganic complexes.
More Related Videos
Related Concept Videos
02:55Exceptions to the Octet Rule
Many covalent molecules have central atoms that do not have eight electrons in their Lewis structures. These molecules fall into three categories:
04:01VSEPR Theory and the Effect of Lone Pairs
Effect of Lone Pairs of Electrons on Molecule Geometry
02:45Valence Bond Theory
Overview of Valence Bond Theory
02:57Coordination Number and Geometry
For transition metal complexes, the coordination number determines the geometry around the central metal ion. Table 1 compares coordination numbers to molecular geometry. The most common structures of the complexes in coordination compounds are octahedral, tetrahedral, and square planar.
02:42Valence Bond Theory
Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
02:46Crystal Field Theory - Tetrahedral and Square Planar Complexes
Tetrahedral 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,...
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,...