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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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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,...
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Chirality is most prevalent in carbon-based tetrahedral compounds, but this important facet of molecular symmetry extends to sp3-hybridized nitrogen, phosphorus and sulfur centers, including trivalent molecules with lone pairs. Here, the lone pair behaves as a functional group in addition to the other three substituents to form an analogous tetrahedral center that can be chiral.
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Thiols and sulfides are sulfur analogs of alcohols and ethers, respectively, where the sulfur atom takes the place of the oxygen atom. Thus, thiols are generally represented as RSH, where R is an alkyl substituent and —SH is the functional group. On the other hand, in sulfides, the central sulfur atom is bonded to two hydrocarbon groups on either side. Depending upon the type of group, sulfides can be either symmetrical or asymmetrical. Both thiols and sulfides display a bent geometry,...
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Complexation Equilibria: The Chelate Effect01:19

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In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
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Sulfides are the sulfur analog of ethers, just as thiols are the sulfur analog of alcohol. Like ethers, sulfides also consist of two hydrocarbon groups bonded to the central sulfur atom. Depending upon the type of groups present, sulfides can be symmetrical or asymmetrical. Symmetrical sulfides can be prepared via an SN2 reaction between 2 equivalents of an alkyl halide and one equivalent of sodium sulfide.
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Structural Preferences in Phosphanylthiolato Platinum(II) Complexes.

Josep Duran1, Alfonso Polo1, Julio Real2

  • 1Departament de Química Universitat de Girona Campus de Montilivi s/n 17071 Girona Spain.

Chemistryopen
|June 17, 2016
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Summary

Researchers explored phosphanylthiolate ligand coordination on platinum(II) complexes. Different ligand-to-platinum ratios unexpectedly yielded distinct platinum complexes, including a novel trinuclear structure.

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Area of Science:

  • Organometallic Chemistry
  • Inorganic Chemistry
  • Computational Chemistry

Background:

  • Platinum(II) complexes are crucial in catalysis and medicine.
  • Controlling the stereochemistry of ligand coordination is vital for tuning complex properties.
  • Phosphanylthiolate ligands offer unique coordination modes.

Purpose of the Study:

  • To investigate the coordination behavior of phosphanylthiolate ligands with platinum(II) centers.
  • To understand the influence of ligand-to-platinum ratios on complex formation.
  • To elucidate the reaction mechanism using computational methods.

Main Methods:

  • Synthesis and structural determination of platinum(II) complexes.
  • Density Functional Theory (DFT) calculations.
  • Conceptual DFT analysis.

Main Results:

  • Coordination with a 2:1 ligand-to-platinum ratio exclusively formed the cis-P,P-bischelate isomer.
  • A ligand-to-platinum ratio of 1:1 resulted in an unexpected trinuclear platinum complex.
  • DFT calculations successfully rationalized the observed reaction pathways and product distributions.

Conclusions:

  • The ligand-to-platinum ratio is a critical factor in directing the stereochemistry of phosphanylthiolate coordination to platinum(II).
  • This study provides a mechanistic understanding of complex formation, enabling control over cis/trans isomerism.
  • The findings open avenues for designing new platinum complexes with tailored structures and potential applications.