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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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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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High-Valent Pyrazolate-Bridged Platinum Complexes: A Joint Experimental and Theoretical Study.

Lorenzo Arnal1, Daniel Escudero2, Sara Fuertes1

  • 1Departamento de Química Inorgánica, Facultad de Ciencias, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC - Universidad de Zaragoza, Pedro Cerbuna 12, 50009 Zaragoza, Spain.

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|August 4, 2022
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Summary

Platinum complexes undergo double oxidative addition with alkyl halides via an SN2 pathway. This study elucidates the reaction mechanisms and characterizes novel platinum(III) and platinum(IV) intermediates, providing insights into high-valent platinum chemistry.

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Area of Science:

  • Organometallic Chemistry
  • Platinum Complexes
  • Reaction Mechanisms

Background:

  • Dimeric platinum complexes with N-heterocyclic carbene ligands were investigated.
  • Understanding the reactivity of platinum complexes with alkyl halides is crucial for synthetic applications.

Purpose of the Study:

  • To investigate the reaction of dimeric platinum complexes with methyl iodide and benzyl bromide.
  • To elucidate the reaction mechanisms using experimental and computational methods.
  • To characterize novel platinum intermediates and products.

Main Methods:

  • Synthesis of platinum complexes and their reactions with alkyl halides.
  • Experimental investigations including single-crystal X-ray diffraction.
  • Density Functional Theory (DFT) calculations to explore reaction pathways.

Main Results:

  • Platinum(II) complexes were converted to platinum(IV) and platinum(III) species upon reaction with methyl iodide and benzyl bromide.
  • The reactions proceed via a two-step SN2 double oxidative addition mechanism.
  • Key intermediates, including platinum(III) species, were proposed and some were synthesized and characterized.

Conclusions:

  • The study provides a detailed mechanistic understanding of the double oxidative addition of alkyl halides to dimeric platinum complexes.
  • Structural and spectroscopic data were obtained for various high-valent platinum complexes, enabling comparisons.
  • The findings contribute to the knowledge of the reactivity and structural diversity of platinum complexes in different oxidation states.