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Crystal Field Theory - Tetrahedral and Square Planar Complexes02:46

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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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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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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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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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Square-Planar Anionic Pt0 Complexes.

Hajime Kameo1, Yudai Tanaka1, Yoshihiro Shimoyama2

  • 1Department of Chemistry, Graduate School of Science, Osaka Metropolitan University Gakuen-cho, Naka-ku, Sakai, Osaka, 599-8531, Japan.

Angewandte Chemie (International Ed. in English)
|February 22, 2023
PubMed
Summary
This summary is machine-generated.

Researchers synthesized a novel T-shaped platinum(0) complex. This platinum complex, stabilized by a diphosphine-borane ligand, allows for the isolation of anionic platinum(0) complexes for the first time.

Keywords:
Anionic ComplexesPhotoelectron SpectroscopyPlatinumX-Ray Diffraction

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Area of Science:

  • Organometallic Chemistry
  • Coordination Chemistry
  • Materials Science

Background:

  • Electron-rich metal complexes are often unstable and difficult to isolate.
  • Stabilizing unusual oxidation states and geometries in metal complexes is a key challenge in chemistry.

Purpose of the Study:

  • To synthesize and characterize a novel T-shaped platinum(0) complex.
  • To investigate the stabilizing effect of a diphosphine-borane ligand on platinum(0).
  • To explore the formation and structural authentication of anionic platinum(0) complexes.

Main Methods:

  • Synthesis of a T-shaped platinum(0) complex featuring a diphosphine-borane ligand.
  • Reaction with Lewis bases to form tetracoordinate complexes.
  • Isolation and structural characterization of anionic platinum(0) complexes using X-ray diffraction.
  • Determination of oxidation state and electronic configuration via X-ray photoelectron spectroscopy and DFT calculations.

Main Results:

  • A T-shaped Pt(0) complex with a diphosphine-borane ligand was successfully prepared.
  • The Pt→B interaction enhanced metal electrophilicity, enabling Lewis base addition.
  • Anionic Pt(0) complexes, [(DPB)PtX]⁻ (X=CN, Cl, Br, I), were isolated and structurally confirmed as square-planar.
  • X-ray photoelectron spectroscopy and DFT calculations confirmed the d¹⁰ configuration and Pt(0) oxidation state.

Conclusions:

  • Coordination of Lewis acids as Z-type ligands is an effective strategy for stabilizing electron-rich metal complexes.
  • This approach allows for the stabilization and isolation of elusive metal complexes with uncommon geometries.
  • The study provides the first structural authentication of anionic Pt(0) complexes.