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1a. (25 pts) on its own separate framework, draw each one of the four v…

Question

1a. (25 pts) on its own separate framework, draw each one of the four vb orbitals belonging to one of the three-center four-electron bonds, in the single resonance form shown below.

Explanation:

Identify the 3c-4e bond

The molecule shown is \(\text{XeOF}_4\). The central xenon atom has a \(3+\) formal charge, an apical oxygen atom with a single bond and a negative charge (\(\text{O}^-\)), and four equatorial fluorine atoms (two covalently bound, and two as isolated fluoride anions \(\text{F}^-\) in this specific resonance structure).

The three-center four-electron (3c-4e) bonding system in this resonance form is formed along the linear \(\text{F}-\text{Xe}-\text{F}\) axes. Specifically, each linear \(\text{F}-\text{Xe}-\text{F}\) unit consists of:

  1. A central xenon atom (\(\text{Xe}^{3+}\)).
  2. Two equatorial fluorine atoms on opposite sides. In this resonance structure, one is covalently bound (sharing a pair of electrons with Xe) and the other is an isolated fluoride ion (\(\text{F}^-\)) with a full octet.

Thus, there are two perpendicular linear 3c-4e systems in the equatorial plane:

  • One along the \(\text{F}-\text{Xe}\cdots\text{F}^-\) axis (left-to-right).
  • One along the other \(\text{F}-\text{Xe}\cdots\text{F}^-\) axis (front-to-back).

Let us focus on one of these linear \(\text{F}-\text{Xe}\cdots\text{F}^-\) 3c-4e bonds to describe its four Valence Bond (VB) orbitals.

Determine the VB orbitals

In Valence Bond theory, a three-center four-electron (3c-4e) bond is described by localized atomic orbitals on each of the three participating atoms. For a linear \(\text{F}_a-\text{Xe}-\text{F}_b\) system:

  • The central \(\text{Xe}\) uses a \(p\)-orbital aligned along the bond axis (let's call it the \(p_x\) orbital).
  • The two terminal fluorine atoms (\(\text{F}_a\) and \(\text{F}_b\)) each use a \(p\)-orbital directed along the bond axis (their respective \(p_x\) orbitals).

The four valence electrons in this 3c-4e system occupy two localized VB orbitals (each containing a pair of electrons):

  1. Covalent Bond Orbital: A localized bonding orbital between \(\text{Xe}\) and the covalently bound fluorine (\(\text{F}_a\)). This is formed by the overlap of the \(\text{Xe}\) \(p_x\) orbital and the \(\text{F}_a\) \(p_x\) orbital.
  2. Fluoride Lone Pair Orbital: A localized non-bonding lone pair orbital residing entirely on the isolated fluoride ion (\(\text{F}_b^-\)). This is a fully occupied \(p_x\) orbital on \(\text{F}_b^-\).

To fully represent the VB description of this resonance structure, we draw the active atomic orbitals that participate in this bonding scheme across the four frameworks:

  • Orbital 1: The \(p\)-orbital on the covalently bound fluorine atom (\(\text{F}\)) pointing toward \(\text{Xe}\).
  • Orbital 2: The \(p\)-orbital on the central \(\text{Xe}\) atom pointing toward the covalently bound fluorine.
  • Orbital 3: The \(p\)-orbital on the central \(\text{Xe}\) atom pointing toward the isolated fluoride ion (\(\text{F}^-\)).
  • Orbital 4: The \(p\)-orbital on the isolated fluoride ion (\(\text{F}^-\)) pointing toward \(\text{Xe}\).

(Note: Orbitals 2 and 3 represent the two lobes of the single \(p\)-orbital on the central \(\text{Xe}\) atom aligned along this axis).

Describe the drawings for each framework

To represen…

Answer:

To represent the four Valence Bond (VB) orbitals belonging to one of the three-center four-electron (3c-4e) bonds along a linear \(\text{F}-\text{Xe}\cdots\text{F}^-\) axis, draw the following atomic orbital components on each of the four frameworks from left to right:

  1. First Framework (Terminal Covalent Fluorine Orbital):

Draw a \(p\)-orbital on the covalently bound equatorial \(\text{F}\) atom, with its lobes aligned along the \(\text{F}-\text{Xe}\) bonding axis pointing toward the central \(\text{Xe}\) atom.

  1. Second Framework (Central Xenon Orbital - Lobe A):

Draw one lobe of the central \(\text{Xe}\) \(p\)-orbital pointing directly along the axis toward the covalently bound equatorial \(\text{F}\) atom.

  1. Third Framework (Central Xenon Orbital - Lobe B):

Draw the second, oppositely phased lobe of the central \(\text{Xe}\) \(p\)-orbital pointing along the axis toward the isolated equatorial \(\text{F}^-\) ion.

  1. Fourth Framework (Terminal Fluoride Ion Orbital):

Draw a fully occupied \(p\)-orbital on the isolated equatorial \(\text{F}^-\) ion, with its lobes aligned along the \(\text{Xe}\cdots\text{F}^-\) axis pointing toward the central \(\text{Xe}\) atom.