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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 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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Metallic bonds are formed between two metal atoms. A simplified model to describe metallic bonding has been developed by Paul Drüde called the “Electron Sea Model”. 
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A hydrogen bond is formed when a weakly positive hydrogen atom already bonded to one electronegative atom (for example, the oxygen in the water molecule) is attracted to another electronegative atom from another polar molecule, such as water (H2O), hydrogen fluoride (HF), or ammonia (NH3). The huge electronegativity difference between the H atom (2.1) and the atom to which it is bonded (4.0 for an F atom, 3.5 for an O atom, or 3.0 for an N atom), combined with the very small size of an H atom...
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Hydrogen bonds are weak attractions between atoms that have formed other chemical bonds. One of these atoms is electronegative, like oxygen, and has a partial negative charge. The other is a hydrogen atom that has bonded with another electronegative atom and has a partial positive charge.
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Because hydrogen has very weak electronegativity when it binds with a strongly electronegative atom, such as oxygen or nitrogen, electrons in the bond are unequally shared....
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Ionic Bonding and Electron Transfer02:48

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Ions are atoms or molecules bearing an electrical charge. A cation (a positive ion) forms when a neutral atom loses one or more electrons from its valence shell, and an anion (a negative ion) forms when a neutral atom gains one or more electrons in its valence shell. Compounds composed of ions are called ionic compounds (or salts), and their constituent ions are held together by ionic bonds: electrostatic forces of attraction between oppositely charged cations and anions. 
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Area of Science:

  • Inorganic Chemistry
  • Computational Chemistry
  • Quantum Chemistry

Background:

  • The interaction force constant of element-hydrogen (E-H) stretching modes in trans-dihydrides is crucial for understanding chemical bonding.
  • Previous studies have not systematically analyzed the sign change of this force constant across different blocks of the periodic table.

Purpose of the Study:

  • To analyze the sign change of the interaction force constant between E-H stretching modes in trans-dihydrides of d-block and p-block elements.
  • To elucidate the electronic origins of this observed reversal in vibrational frequencies.
  • To investigate the trend of these interactions down specific groups and in transition states of hydride transfer reactions.

Main Methods:

  • Density Functional Theory (DFT) calculations were employed to study the energetics of isoelectronic triatomic [H-M-H] and [H-E-H] systems.
  • Analysis of vibrational frequencies (νsym and νasym) to determine the interaction force constant.
  • Investigation of model compounds (trans-NiH₂(porphyrin) and trans-EH₂(porphyrin)) in their singlet states to examine hydride transfer transition states.

Main Results:

  • A sign change in the interaction force constant was observed as transition metals (M) approach Group 12 elements.
  • The symmetric (νsym) and antisymmetric (νasym) vibration energies approach each other for M in Group 12, but νsym drops below νasym for Group 13 elements (E).
  • The magnitude of interaction (νgap) increases down Groups 11, 12, and 14, remaining constant for Group 13. This reversal is also present in hydride transfer transition states.

Conclusions:

  • The observed reversal in vibrational mode energies is attributed to the role of d-orbitals in H-M-H bonding versus their nonbonding character in H-E-H compounds.
  • DFT calculations successfully model the electronic and energetic trends governing these interactions.
  • The findings provide insights into the reactivity of dihydrides in reactions like hydride transfer.