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Valence Bond Theory02:42

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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...
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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,...
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In most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...
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Crystal Field Theory
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...
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Many covalent molecules have central atoms that do not have eight electrons in their Lewis structures. These molecules fall into three categories:
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Color in Coordination Complexes
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...
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Nickel-Borolide Complexes and Their Complex Electronic Structure.

Sam Yruegas1, Hao Tang2, Gayle Z Bornovski2

  • 1Department of Chemistry and Biochemistry, Baylor University, One Bear Place #97348, Waco, Texas 76798, United States.

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|October 12, 2021
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Summary
This summary is machine-generated.

Borolides, dianionic heterocyclic analogues of cyclopentadienides, form unique nickel complexes. These complexes exhibit distinct electronic structures and rapid sequential oxidation, differing significantly from metallocenes.

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Area of Science:

  • Organometallic Chemistry
  • Boron Chemistry
  • Heterocyclic Chemistry

Background:

  • Borolides (BC4^2-) are dianionic heterocyclic analogues to monoanionic cyclopentadienides.
  • Both ligand types are formally considered six-π-electron donors in organometallic complexes.
  • Significant differences in electronic structure and properties exist between borolide and cyclopentadienide metal complexes.

Purpose of the Study:

  • To investigate and compare the electronic structure of transition metal complexes featuring borolides versus cyclopentadienides.
  • To characterize the electrochemical properties of a novel nickel-borolide sandwich complex.
  • To understand the factors contributing to unusual redox behavior in these systems.

Main Methods:

  • Synthesis and characterization of the 18-electron sandwich complex Ni(iPr2NBC4Ph2)2 (1).
  • Structural analysis of the complex, including the angle between Ni-B-N planes.
  • Electrochemical studies (cyclic voltammetry) to determine oxidation potentials.

Main Results:

  • The nickel-borolide complex Ni(iPr2NBC4Ph2)2 (1) exhibits an approximately 90° angle between Ni-B-N planes.
  • The electronic structure is best described by resonance, with a major contribution from Ni^2+ and two monoanionic radical (BC4^•-) ligands.
  • Compound 1 shows two sequential one-electron oxidations within a narrow potential range (<0.2 V).

Conclusions:

  • Borolide ligands induce significantly different electronic structures and properties in transition metal complexes compared to cyclopentadienides.
  • The observed rapid sequential oxidation in the nickel-borolide complex contrasts sharply with the behavior of metallocenes.
  • The electronic configuration and resonance stabilization play a crucial role in the unique electrochemical properties of borolide complexes.