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Related Concept Videos

Properties of Transition Metals02:58

Properties of Transition Metals

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Transition metals are defined as those elements that have partially filled d orbitals. As shown in Figure 1, the d-block elements in groups 3–12 are transition elements. The f-block elements, also called inner transition metals (the lanthanides and actinides), also meet this criterion because the d orbital is partially occupied before the f orbitals.
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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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The Periodic Table03:25

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As early chemists discovered more elements, they realized that various elements could be grouped by their similar chemical behaviors. One such grouping includes lithium (Li), sodium (Na), and potassium (K). All of these elements are shiny, conduct heat and electricity well, and have similar chemical properties. A second grouping includes calcium (Ca), strontium (Sr), and barium (Ba), which also are shiny, good conductors of heat and electricity, and have chemical properties in common. However,...
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Periodic Classification of the Elements04:00

Periodic Classification of the Elements

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The periodic table arranges atoms based on increasing atomic number so that elements with the same chemical properties recur periodically. When their electron configurations are added to the table, a periodic recurrence of similar electron configurations in the outer shells of these elements is observed. Because they are in the outer shells of an atom, valence electrons play the most important role in chemical reactions. The outer electrons have the highest energy of the electrons in an atom...
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Application of Elemental Lanthanides in the Selective C-F Activation of Trifluoromethylated Benzofulvenes Providing Access to Various Difluoroalkenes
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Lanthanide Photocatalysis.

Yusen Qiao1, Eric J Schelter1

  • 1P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry , University of Pennsylvania , 231 S. 34th Street , Philadelphia , Pennsylvania 19104 , United States.

Accounts of Chemical Research
|October 19, 2018
PubMed
Summary
This summary is machine-generated.

Earth-abundant lanthanide photocatalysts, particularly cerium complexes, offer potent alternatives to precious metals for organic synthesis. These catalysts enable challenging C-C bond formations and dehalogenation reactions via single-electron transfer (SET) under mild conditions.

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Area of Science:

  • Inorganic Chemistry
  • Photocatalysis
  • Organic Synthesis

Background:

  • Rare and precious metal photosensitizers are often used in photocatalysis but are expensive and scarce.
  • Lanthanide photocatalysts offer a sustainable and cost-effective alternative, utilizing earth-abundant elements.
  • Lanthanides can generate reactive species via single-electron transfer (SET) and hydrogen atom transfer (HAT) pathways.

Purpose of the Study:

  • To explore the rational design and application of lanthanide photo(redox)catalysis.
  • To understand the photophysics of lanthanide luminophores for photocatalytic applications.
  • To develop potent cerium-based photocatalysts for challenging organic transformations.

Main Methods:

  • Structural, spectroscopic, and computational studies of cerium complexes.
  • Photophysical and photochemical investigations of Ce(III) and Ce(IV) species.
  • Evaluation of catalytic activity in C-C bond formation, dehalogenation, and borylation reactions.

Main Results:

  • Luminescent Ce(III) guanidinate-amide complexes mediate photocatalytic C(sp³)-C(sp³) bond formation via excited-state reduction.
  • Structure-property relationships were established, correlating ligand type and steric hindrance with emission color and quantum yield.
  • Hexachlorocerate(III) anion ([CeIIICl6]3-) acts as a potent UVA photoreductant for dehalogenation and borylation of aryl chlorides.

Conclusions:

  • Lanthanide photo(redox)catalysis, particularly using cerium, provides a powerful platform for organic synthesis.
  • Cerium photocatalysts exhibit strong reducing power and tunable photophysical properties.
  • These findings pave the way for practical applications in organic synthesis, pharmaceutical development, and small molecule activation.