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Related Concept Videos

Structural Isomerism02:34

Structural Isomerism

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Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can...
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Stereoisomerism02:52

Stereoisomerism

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Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
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Electron Configuration of Multielectron Atoms03:26

Electron Configuration of Multielectron Atoms

65.9K
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...
65.9K
Valence Bond Theory02:42

Valence Bond Theory

11.5K
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...
11.5K
Crystal Field Theory - Tetrahedral and Square Planar Complexes02:46

Crystal Field Theory - Tetrahedral and Square Planar Complexes

49.3K
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,...
49.3K
Crystal Field Theory - Octahedral Complexes02:58

Crystal Field Theory - Octahedral Complexes

31.4K
Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
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Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene
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Cerium(IV) Imido Complexes: Structural, Computational, and Reactivity Studies.

Lukman A Solola1, Alexander V Zabula1, Walter L Dorfner1

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

Journal of the American Chemical Society
|January 13, 2017
PubMed
Summary
This summary is machine-generated.

Alkali metal cations influence cerium(IV) imido complex geometry, shortening the Ce═N bond with increasing cation size. A novel unsupported Ce═N bond was achieved, with DFT revealing 5d orbital contributions to bonding.

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Area of Science:

  • Inorganic Chemistry
  • Organometallic Chemistry
  • Materials Science

Background:

  • Cerium(IV) imido complexes are of interest due to their unique bonding and reactivity.
  • Understanding the influence of alkali metal counterions on these complexes is crucial for designing new materials and catalysts.

Purpose of the Study:

  • To synthesize and characterize a series of alkali metal capped cerium(IV) imido complexes.
  • To investigate the structural impact of alkali metal counterions on the cerium-nitrogen bond.
  • To explore the reactivity of these novel cerium complexes.

Main Methods:

  • Synthesis and full characterization of alkali metal capped cerium(IV) imido complexes.
  • X-ray structural investigation to determine the impact of counterions on complex geometry.
  • Density Functional Theory (DFT) calculations to elucidate electronic structure and bonding.
  • Reactivity studies involving silicon-oxygen bond cleavage and reactions with benzophenone.

Main Results:

  • Isolation and characterization of [M(solv)x][Ce═N(3,5-(CF3)2C6H3)(TriNOx)] complexes (M = Li, K, Rb, Cs).
  • Observed shortening of the Ce═N bond with increasing alkali metal cation size.
  • Isolation of the first unsupported, terminal Ce(IV)═N multiple bond complex with a Cs+ counterion and 2.2.2-cryptand, featuring a Ce═N bond length of 2.077(3) Å.
  • DFT studies indicated a significant contribution from the cerium 5d orbital to the Ce═N bonds.
  • Demonstrated reactivity, including Si-O bond cleavage by a potassium complex and formation of a rare Ce(IV)-oxo complex from a rubidium complex.

Conclusions:

  • Alkali metal counterions play a significant role in tuning the structure and bonding of cerium(IV) imido complexes.
  • The ability to form unsupported terminal Ce(IV)═N bonds opens new avenues in cerium chemistry.
  • These complexes exhibit interesting reactivity, highlighting their potential applications in catalysis and materials science.