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Related Concept Videos

Valence Bond Theory02:42

Valence Bond Theory

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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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Complexation Equilibria: Overview01:23

Complexation Equilibria: Overview

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Complexation reactions take place when dative or coordinate covalent bonds form between metal ions and ligands. The compounds formed in these reactions are called coordination compounds. The number of bonds formed between the metal ion and the ligands is called its coordination number. Generally, most metal ions in an aqueous solution are solvated by water molecules and thus exist as aqua complexes.
The equilibrium constant of the complexation reaction is represented as the formation constant...
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Hydrogen Bonds01:04

Hydrogen Bonds

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A hydrogen bond is formed when a weakly positive hydrogen atom already bonded to one electronegative atom (for example, the oxygen in the water molecule) is attracted to another electronegative atom from another polar molecule, such as water (H2O), hydrogen fluoride (HF), or ammonia (NH3). The huge electronegativity difference between the H atom (2.1) and the atom to which it is bonded (4.0 for an F atom, 3.5 for an O atom, or 3.0 for an N atom), combined with the very small size of an H atom...
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Hydrogen Bonds00:26

Hydrogen Bonds

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Hydrogen bonds are weak attractions between atoms that have formed other chemical bonds. One of these atoms is electronegative, like oxygen, and has a partial negative charge. The other is a hydrogen atom that has bonded with another electronegative atom and has a partial positive charge.
Hydrogen Bonds Control the World!
Because hydrogen has very weak electronegativity when it binds with a strongly electronegative atom, such as oxygen or nitrogen, electrons in the bond are unequally shared....
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Hybridization of Atomic Orbitals II03:35

Hybridization of Atomic Orbitals II

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sp3d and sp3d 2 Hybridization
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Complexation Equilibria: The Chelate Effect01:19

Complexation Equilibria: The Chelate Effect

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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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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
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Synthesis, characterization, and computational study of complexes containing Pt···H hydrogen bonding interactions.

Miguel Baya1, Ursula Belío, Antonio Martín

  • 1Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), Departamento de Química Inorgánica, Universidad de Zaragoza-CSIC , 50009 Zaragoza, Spain.

Inorganic Chemistry
|December 17, 2013
PubMed
Summary

New platinum complexes exhibit strong Pt···H-O hydrogen bonds in both solution and solid states, confirmed by NMR, X-ray diffraction, and DFT calculations. These interactions show partial covalency and lead to unexpected trinuclear complex formation upon deprotonation.

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Area of Science:

  • Organometallic Chemistry
  • Supramolecular Chemistry
  • Crystallography

Background:

  • Platinum complexes with fluorinated ligands are of interest due to their unique electronic properties.
  • Hydrogen bonding plays a crucial role in molecular recognition and self-assembly.
  • Understanding metal-ligand interactions is key to designing novel functional materials.

Purpose of the Study:

  • To synthesize and characterize novel platinum(II) complexes with 7,8-benzoquinolinate and 8-hydroxyquinoline derivatives.
  • To investigate the presence and nature of Pt···H-O hydrogen bonds in these complexes.
  • To explore the structural and electronic consequences of these interactions and subsequent deprotonation.

Main Methods:

  • Synthesis of platinum complexes [Pt(C6F5)(bzq)L] via ligand substitution.
  • Characterization using 1H NMR spectroscopy and X-ray diffraction analysis.
  • Theoretical calculations including Density Functional Theory (DFT) and Atoms In Molecules (AIM) topological analyses.
  • Deprotonation studies using n-butyllithium (BuLi) followed by structural analysis of resulting trinuclear complexes.

Main Results:

  • Successful synthesis of complexes 1 and 2, featuring Pt···H-O hydrogen bonds confirmed by downfield hydroxyl proton shifts and Pt-H coupling in NMR.
  • X-ray diffraction studies corroborated the presence of Pt···H-O hydrogen bonds in the solid state for complexes 1 and 2.
  • DFT calculations and AIM analyses revealed these interactions as electrostatic with partial covalency, supported by bond paths and critical point data.
  • Deprotonation led to unexpected trinuclear complexes (3 and 4) with altered coordination modes.

Conclusions:

  • The study demonstrates the formation and characterization of platinum complexes with significant Pt···H-O hydrogen bonding.
  • Both solution and solid-state evidence, alongside theoretical calculations, confirms the nature of these interactions.
  • The deprotonation pathway offers a route to novel multinuclear platinum-lithium architectures.