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Electron Configurations02:46

Electron Configurations

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Electron configurations and orbital diagrams can be determined by applying the Aufbau principle (each added electron occupies the subshell of lowest energy available), Pauli exclusion principle (no two electrons can have the same set of four quantum numbers), and Hund’s rule of maximum multiplicity (whenever possible, electrons retain unpaired spins in degenerate orbitals).
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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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The alkali metal sodium (atomic number 11) has one more electron than the neon atom. This electron must go into the lowest-energy subshell available, the 3s orbital, giving a 1s22s22p63s1 configuration. The electrons occupying the outermost shell orbital(s) (highest value of n) are called valence electrons, and those occupying the inner shell orbitals are called core electrons. Since the core electron shells correspond to noble gas electron configurations, we can abbreviate electron...
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Metallic solids such as crystals of copper, aluminum, and iron are formed by metal atoms. The structure of metallic crystals is often described as a uniform distribution of atomic nuclei within a “sea” of delocalized electrons. The atoms within such a metallic solid are held together by a unique force known as metallic bonding that gives rise to many useful and varied bulk properties.
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For transition metal complexes, the coordination number determines the geometry around the central metal ion. Table 1 compares coordination numbers to molecular geometry. The most common structures of the complexes in coordination compounds are octahedral, tetrahedral, and square planar.
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Inserting Three-Coordinate Nickel into [4Fe-4S] Clusters.

Majed S Fataftah1, Daniel W N Wilson1, Zachary Mathe2

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|October 28, 2024
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Summary
This summary is machine-generated.

Researchers demonstrate how electron transfer can assemble complex nickel-iron-sulfide clusters, mimicking the active site of carbon monoxide dehydrogenase (CODH). This reveals a novel pathway for forming [1Ni-4Fe-4S] and [2Ni-3Fe-4S] clusters, highlighting Ni1+ viability in these systems.

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Area of Science:

  • Bioinorganic Chemistry
  • Metalloenzyme active site synthesis
  • Nickel-Iron-Sulfur cluster assembly

Background:

  • Metalloenzymes catalyze crucial redox reactions, including CO2/CO interconversion, under mild conditions.
  • Anaerobic carbon monoxide dehydrogenase (CODH) utilizes a unique [NiFe3S4]-Feu cluster with a three-coordinate nickel site.
  • The natural assembly mechanism of the CODH C-cluster remains poorly understood.

Purpose of the Study:

  • To investigate the assembly of nickel-iron-sulfur clusters relevant to the CODH C-cluster.
  • To explore the role of electron transfer in driving the formation of complex metalloenzyme active sites.
  • To demonstrate the viability of Ni1+ within iron-sulfur cluster environments.

Main Methods:

  • Synthesis of novel nickel-iron-sulfur clusters using Ni0 precursors and [Fe4S4]3+ clusters.
  • Characterization via magnetometry, electron paramagnetic resonance (EPR), Mössbauer, and X-ray absorption spectroscopy.
  • Theoretical validation using density functional theory (DFT) computations.

Main Results:

  • Electron transfer drives Ni0 insertion into [Fe4S4]3+, forming a [1Ni-4Fe-4S] cluster with an external Ni1+.
  • Modification of the Ni0 precursor leads to insertion of two Ni atoms and ejection of one Fe, forming an unprecedented [2Ni-3Fe-4S] cluster.
  • Both synthesized clusters feature three-coordinate metal sites and Ni in the +1 oxidation state, confirmed by spectroscopy and DFT.

Conclusions:

  • Redox-driven transformations can assemble complex, higher-nuclearity nickel-iron-sulfur clusters.
  • Ni1+ is a stable and viable oxidation state within iron-sulfur cluster frameworks.
  • These findings provide insights into the potential assembly pathways for the CODH C-cluster active site.