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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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The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
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A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...
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In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...
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Coordination Compounds and Nomenclature02:54

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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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Author Spotlight: A Rapid, Microwave-Assisted Hydrothermal Synthesis Of Nickel Hydroxide Nanosheets
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Hydrogen-bonded nickel(I) complexes.

Jessica R Wilson1, Matthias Zeller2, Nathaniel K Szymczak1

  • 1Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109, USA. nszym@umich.edu.

Chemical Communications (Cambridge, England)
|December 21, 2020
PubMed
Summary
This summary is machine-generated.

Researchers synthesized nickel complexes with hydrogen bonds to halides. This enabled the creation and characterization of a unique nickel(i) fluoride complex stabilized by these hydrogen bonds.

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Area of Science:

  • Coordination Chemistry
  • Organometallic Chemistry
  • Supramolecular Chemistry

Background:

  • Nickel complexes with tris(2-pyridylmethyl)amine (TPA) ligands are important in catalysis and bioinorganic chemistry.
  • Hydrogen bonding plays a crucial role in stabilizing reactive intermediates and influencing molecular structure.
  • The synthesis and characterization of low-valent nickel species, particularly nickel(i), remain challenging.

Purpose of the Study:

  • To synthesize novel nickel(ii) tris(2-pyridylmethyl)amine (TPA) complexes incorporating hydrogen bond donors.
  • To investigate the influence of halide-appended hydrogen bonds on the electronic and structural properties of nickel complexes.
  • To achieve the reduction to nickel(i) and characterize the resulting nickel(i) fluoride species.

Main Methods:

  • Synthesis of nickel(ii) complexes with TPA ligands functionalized with hydrogen-bonding groups.
  • Characterization of the synthesized nickel(ii) complexes using spectroscopic techniques (e.g., NMR, UV-Vis) and X-ray crystallography.
  • Electrochemical reduction to the nickel(i) state followed by structural and spectroscopic analysis of the reduced species.

Main Results:

  • A series of nickel(ii) TPA complexes with appended hydrogen bonds to fluoride, chloride, and bromide were successfully synthesized.
  • Reduction to the nickel(i) state yielded an unprecedented nickel(i) fluoride complex.
  • The nickel(i) fluoride complex was stabilized by the appended hydrogen bonds, allowing for detailed structural and spectroscopic characterization.

Conclusions:

  • Appended hydrogen bonds are effective in stabilizing nickel complexes, including reactive low-valent states.
  • The study demonstrates a viable strategy for accessing and characterizing unusual nickel(i) fluoride complexes.
  • This work provides insights into the role of non-covalent interactions in stabilizing transition metal species.