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Ch.23 - Transition Metals and Coordination Chemistry
Chapter 23, Problem 52b

The lobes of which d orbitals point directly between the ligands in b. tetrahedral geometry?

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1
Identify the geometry of the molecule in question, which is tetrahedral in this case.
Recall that in tetrahedral geometry, the ligands are positioned at the corners of a tetrahedron with bond angles of approximately 109.5 degrees.
Understand that d orbitals in an atom are shaped differently and include the d_xy, d_xz, d_yz, d_x^2-y^2, and d_z^2 orbitals.
Analyze which d orbitals would have lobes pointing directly between the ligands in a tetrahedral arrangement. This requires visualizing the orientation of the lobes relative to the positions of the ligands.
Conclude that the d orbitals with lobes pointing directly between the ligands in tetrahedral geometry are d_xy, d_xz, and d_yz, as their lobes point towards the edges of the tetrahedron rather than directly at the corners where the ligands are located.

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Key Concepts

Here are the essential concepts you must grasp in order to answer the question correctly.

Tetrahedral Geometry

Tetrahedral geometry is a molecular shape that arises when a central atom is surrounded by four other atoms or groups of atoms, positioned at the corners of a tetrahedron. In this arrangement, the bond angles are approximately 109.5 degrees, minimizing electron pair repulsion according to VSEPR theory. This geometry is commonly observed in molecules like methane (CH4) and is crucial for understanding the spatial arrangement of ligands around a central atom.
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Electron Geometry

d Orbitals

d orbitals are a set of five atomic orbitals that can hold a maximum of ten electrons. They are important in transition metals and play a significant role in bonding and the formation of complex ions. In tetrahedral coordination, the relevant d orbitals (specifically dxy, dyz, and dxz) are oriented such that their lobes point between the ligands, facilitating effective overlap and bonding interactions.
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d Orbital Orientations

Ligand Field Theory

Ligand Field Theory (LFT) is an extension of crystal field theory that describes the electronic structure of transition metal complexes. It considers the effects of ligands on the energy levels of d orbitals, leading to splitting patterns that influence the geometry and reactivity of the complex. In tetrahedral complexes, the d orbitals split into two sets, with the lower-energy orbitals being those that point between the ligands, which is essential for understanding the bonding in such geometries.
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Strong-Field Ligands result in a large Δ and Weak-Field Ligands result in a small Δ.
Related Practice
Open Question
Complete the exercises below. a. A complex absorbs photons with an energy of 4.51 x 10⁻¹⁹ J. What is the wavelength of these photons? b. If this is the only place in the visible spectrum where the complex absorbs light, what color would you expect the complex to be?
Open Question
Complete the exercises below. Identify each of the following coordination complexes as either diamagnetic or paramagnetic: a. [ZnCl₄]²⁻ b. [Pd(NH₃)₂ Cl₂]
Textbook Question

The lobes of which d orbitals point directly between the ligands in a. octahedral geometry,

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Open Question
Complete the exercises below. a. Sketch a diagram that shows the definition of the crystal-field splitting energy (∆) for an octahedral crystal-field. b. What is the relationship between the magnitude of ∆ and the energy of the d-d transition for a d¹ complex? c. Calculate ∆ in kJ/mol if a d¹ complex has an absorption maximum at 545 nm.
Textbook Question

As shown in Figure 23.26, the d-d transition of [Ti(H2O)6]³⁺ produces an absorption maximum at a wavelength of about 500 nm .


a. What is the magnitude of ∆ for [Ti(H2O)6]³⁺ in kJ/mol?


b. How would the magnitude of ∆ change if the H2O ligands in [Ti(H2O)6]]³⁺ were placed with NH3 ligands?

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Open Question
Complete the exercises below. Give the number of (valence) d electrons associated with the central metal ion in each of the following complexes: a. K₃ [TiCl₆], b. Na₃ [Co(NO₂)₆], c. [Ru(en)₃] Br₃, d. [Mo(EDTA)] ClO₄, e. K₃ [ReCl₆].