Chapter 20: Problem 114
Match the list I and II, pick the correct matching from the codes given below List I (a) \(\left[\mathrm{Ag}(\mathrm{CN})_{2}\right]\) (b) \(\left[\mathrm{Cu}\left(\mathrm{CN}_{4}\right)\right]^{3}\) (c) \(\left[\mathrm{Cu}(\mathrm{CN})_{6}\right]^{3-}\) (d) \(\left[\mathrm{Cu}\left(\mathrm{NH}_{3}\right)_{4}\right]^{2+}\) (e) \(\left[\mathrm{Fe}(\mathrm{CN})_{6}\right]^{-}\) List II 1\. square planar and \(1.73 \mathrm{BM}\) 2\. linear and zero 3\. octahedral and zero 4\. tetrahedral and zero 5\. octahedral and \(1.73\) BM (a) a-4, b-2, c-5, d-3, e-1 (b) a-4, b-5, c-2, d-1, e-3 (c) a-2, b-4, c-5, d-1, e-3 (d) a-5, b-4, c-1, d-3, e-2
Short Answer
Step by step solution
Analyzing the Structure - List I(a)
Identifying the Structure - List I(b)
Determining Geometry - List I(c)
Examining Structure - List I(d)
Analyzing Geometry - List I(e)
Matching with List II
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Key Concepts
These are the key concepts you need to understand to accurately answer the question.
Complex Geometry
- Linear geometry: Occurs when two ligands are present, as seen in \([\text{Ag(CN)}_2]\). Here, the silver and cyanide ions form a straight line, leading to no geometric spatial effect that would generally allow unpaired electrons. As a result, these complexes usually have a zero magnetic moment.
- Square planar geometry: This is common for complexes with four ligands, such as \([\text{Cu(NH}_3)_4]^{2+}\), where the ligands are located at the corners of a square around the metal. The electron arrangements in this configuration can lead to partial unpaired electrons, contributing to magnetic moments like 1.73 BM.
- Tetrahedral geometry: Like square planar, tetrahedral complexes contain four ligands but differ as they form a triangular pyramid. This can sometimes result with zero magnetic moment when electrons pair thoroughly.
- Octahedral geometry: With six ligands, these complexes, such as \([\text{Fe(CN)}_6]^{-}\), offer room for various arrangements that generally promote electron pairing, leading to no magnetic moment.
Magnetic Moments
- Zero magnetic moment: Common in environments supporting electron pairing, such as octahedral complexes, which accommodate six ligands around the central metal, as seen in \([\text{Cu(CN)}_6]^{3-}\). Efficient pairing leads to no unpaired electrons, hence zero magnetic moment.
- Non-zero magnetic moment: Complexes like the square planar \([\text{Cu(NH}_3)_4]^{2+}\) exhibit magnetic moments, evidenced by 1.73 BM. Here, unpaired electrons remain due to how electronic configuration and ligand-field splitting create inequivalent d-orbitals.
Ligands
- Cyanide (CN\(^-\)): A strong field ligand producing considerable field splitting, often leading to low-spin complexes, which results in electron pairing. This is illustrated in complexes like \([\text{Fe(CN)}_6]^{-}\) that have an octahedral shape and zero magnetic moment.
- Ammonia (NH\(_3\)): A moderate field ligand, as seen in \([\text{Cu(NH}_3)_4]^{2+}\) which forms square planar geometry and may show non-zero magnetic moments due to less field splitting allowing some unpaired electrons.
Electronic Structure
- d-Orbital splitting: In complexes, ligands affect the energy levels of the d-orbitals. The extent of this splitting is influenced by the ligand's field strength, altering the electrons' distribution. For instance, strong field ligands like CN\(^-\) produce substantial splitting, leading to paired electrons often forming low-spin complexes such as \([\text{Fe(CN)}_6]^{-}\) with zero magnetic moment.
- High-spin vs Low-spin: When ligands cause less d-orbital splitting, resulting complexes may be high-spin, having a larger number of unpaired electrons. Conversely, significant splitting leads to low-spin states, favoring paired electrons. Whether a complex is high- or low-spin vastly influences its color, reactivity, and magnetism.