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Chapter 20: Problem 119

Which of the following statements is/are correct regarding metal carbonyl? (a) \(\operatorname{In} \mathrm{Fe}_{3}(\mathrm{CO})_{12}\) no. of \(\mathrm{Fe}-\mathrm{Fe}\) bonds are 3 (b) In \(\mathrm{Mn}_{2}(\mathrm{CO})_{10}\) bond order of \(\mathrm{Mn}-\mathrm{Mn}\) is 0 (c) \(\mathrm{Fe}(\mathrm{CO})_{5}\) is diamagnetic (d) In \(\mathrm{Fe}_{2}(\mathrm{CO})_{4}\) all bond length are same

Short Answer

Expert verified
Statements (a) and (c) are correct.

Step by step solution

01

Analyze Fe3(CO)12

First, evaluate the compound Fe3(CO)12. In this complex, iron is in low oxidation state and CO ligands are strong field ligands bringing different iron atoms together. This complex typically has an cluster structure with Fe-Fe bonds. Thus, statement (a) is generally correct, as this complex can have Fe-Fe bonds, often observed as three.
02

Evaluate Mn2(CO)10 Bond Order

The Mn2(CO)10 complex is a dimer like structure, with each Mn having a 3d5 4s2 electron configuration. The Mn-Mn bond order can be derived from the number of shared pairs of electrons. Upon considering the electron sharing through carbonyl bridge, it turns out to create a bond order of one between Mn atoms, not zero. Hence, statement (b) is incorrect.
03

Determine Magnetism in Fe(CO)5

Fe(CO)5 is an iron carbonyl complex with Fe in zero oxidation state, and CO being a strong field ligand. This results in all the electrons being paired due to the low-spin configuration. Therefore, statement (c) is correct because the complex is diamagnetic.
04

Review Bond Lengths in Fe2(CO)4

For Fe2(CO)4, typically all the CO ligands are equivalent, suggesting possible equivalence in bond lengths due to electronic configuration and ligand symmetry. However, Fe2(CO)4 is not a typical or stable carbonyl, possibly raising structure complexity issues resulting in varied bond lengths, hence statement (d) should be considered incorrect.

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Key Concepts

These are the key concepts you need to understand to accurately answer the question.

Fe3(CO)12
Metal carbonyl complexes often showcase intriguing structures, and \( ext{Fe}_3( ext{CO})_{12}\) is no exception. This compound is known for its cluster-like formation. The iron atoms are in a low oxidation state, and are linked by bridging carbonyl (CO) ligands. Each iron atom bonds to the carbonyl groups, leading to a structure where they are held close together. Consequently, \( ext{Fe}_3( ext{CO})_{12}\) typically exhibits three \( ext{Fe}- ext{Fe}\) bonds. These bonds are a result of the metallic center interacting through the \( ext{CO}\) ligands, illustrating the complex communication within metal clusters.
Mn2(CO)10
The compound \( ext{Mn}_2( ext{CO})_{10}\) presents an illustration of how bonding changes in metal carbonyls. It forms a dimer structure with \( ext{Mn}- ext{Mn}\) connections. Each manganese in \( ext{Mn}_2( ext{CO})_{10}\) has an electron configuration of 3d5 4s2. Carbonyl ligands act as bridges that modulate the interaction between the manganese atoms. Unlike some early assumptions, the \( ext{Mn}- ext{Mn}\) bond order isn't zero. Instead, the counting and sharing of the electrons through the carbonyl bridges often result in a bond order of one. This demonstrates how carbonyl bridges can complicate direct metal-metal bond evaluations in dimers.
Fe(CO)5
The \( ext{Fe}( ext{CO})_5\) compound is an archetypical example of a zero oxidation state metal carbonyl. The carbonyl ligands here act as strong field ligands, engaging in backbonding with the iron atom which is crucial for stability. Electron pairing occurs as a result of these strong field interactions, leading to a low-spin state. Consequently, the iron becomes diamagnetic because all electrons are paired. This interesting characteristic of \( ext{Fe}( ext{CO})_5\) stems from its unique geometry where iron resides in the center surrounded by five carbonyl groups similar to a trigonal bipyramidal shape.
Bond Order
Bond order characterizes the strength and number of bonds between two atoms. In metal carbonyl compounds such as \( ext{Mn}_2( ext{CO})_{10}\), determining the bond order between metal centers is pivotal. The bond order is approximated by considering electron sharing. Various interactions, including those contributed by ligand bridges like \( ext{CO}\), play a vital role in calculating bond orders. A higher bond order signifies a stronger bonding interaction. For instance, the bond order of \( ext{Mn}- ext{Mn}\) in \( ext{Mn}_2( ext{CO})_{10}\) is typically one, denoting a moderate strength bond facilitated by shared electron pairs through carbonyl bridges.
Diamagnetism
Diamagnetism is a property of compounds that results from the pairing of electrons. In the context of metal carbonyls, this occurs when all the electrons in a metal are paired, leading to no net magnetic moment. For \( ext{Fe}( ext{CO})_5\), the low-spin state induced by strong field ligands, such as \( ext{CO}\), ensures that the electron configuration is fully paired. Therefore, \( ext{Fe}( ext{CO})_5\) exhibits diamagnetism due to its symmetrical configuration and effective electron pairing. Understanding diamagnetism in these complexes is important as it reflects the interactions and electron arrangements facilitated by the ligands.
Fe-Fe Bonds
Understanding the formation of \( ext{Fe}- ext{Fe}\) bonds provides insights into cluster-based metal carbonyls. In \( ext{Fe}_3( ext{CO})_{12}\), these bonds are prevalent and are essential for maintaining the complex's structure. The \( ext{Fe}- ext{Fe}\) bonds are supported by bridging carbonyls, enabling the sharing of electrons across the metal centers. Such interactions are considered as coordination within the cluster, where the mechanical stability is provided by these metal-metal bonds. The formation of \( ext{Fe}- ext{Fe}\) bonds in a multi-center environment enriches our understanding of metal-metal bonding in solid-state chemistry.

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Most popular questions from this chapter

Which of the following statement is incorrect? (a) in \(\mathrm{K}_{3}\left[\mathrm{Fe}(\mathrm{CN})_{6}\right]\), the ligand has satisfied both primary and secondary valencies of ferric ion (b) in \(\mathrm{K}_{3}\left[\mathrm{Fe}(\mathrm{CN})_{6}\right]\) the ligand has satisfied only the secondary valency of ferric ion (c) in \(\mathrm{K}_{4}\left[\mathrm{Fe}(\mathrm{CN})_{6}\right]\) the ligand has satisfied both primary and secondary valencies of ferrous ion (d) in \(\left[\mathrm{Cu}\left(\mathrm{NH}_{3}\right)_{4}\right] \mathrm{SO}_{4}\), the ligand has satisfied only the secondary valency of copper

The coordination number and oxidation number of \(\mathrm{M}\) in the compound \(\left[\mathrm{M}\left(\mathrm{SO}_{4}\right)\left(\mathrm{NH}_{3}\right)_{5}\right]\) will be (a) 6 and 3 (b) 2 and 6 (c) 6 and 2 (d) 3 and 6

Which of the following facts about the complex \(\left[\mathrm{Cr}\left(\mathrm{NH}_{3}\right)_{6}\right] \mathrm{Cl}_{3}\) is wrong? (a) The complex gives white precipitate with silver nitrate solution. (b) The complex involves \(\mathrm{d}^{2} \mathrm{sp}^{3}\) hybridisation, and is octahedral in shape. (c) The complex is an outer orbital complex. (d) The complex is paramagnetic.

The 'spin-only' magnetic moment [in units of Bohr magneton \(\left.\left(\mu_{\mathrm{B}}\right)\right]\) of \(\mathrm{Ni}^{2+}\) in aqueous solution would be (Atomic number of \(\mathrm{Ni}=28\) ) (a) \(2.84\) (b) \(4.90\) (c) 0 (d) \(1.73\)

Among \(\left[\mathrm{Ni}(\mathrm{CO})_{4}\right],\left[\mathrm{Ni}(\mathrm{CN})_{4}\right]^{2-}\) and \(\left[\mathrm{NiCl}_{4}\right]^{2-}\) (a) \(\left[\mathrm{Ni}(\mathrm{CO})_{4}\right]\) and \(\left[\mathrm{NiCl}_{4}\right]^{2}\) are diamagnetic and \(\left[\mathrm{Ni}(\mathrm{CN})_{4}\right]^{2}\) is paramagnetic (b) \(\left[\mathrm{NiCl}_{4}\right]^{2-}\) and \(\left[\mathrm{Ni}(\mathrm{CN})_{4}\right]^{2-}\) are diamagnetic and \(\left[\mathrm{Ni}(\mathrm{CO})_{4}\right]\) is paramagnetic (c) \(\left[\mathrm{Ni}(\mathrm{CO})_{4}\right]\) and \(\left[\mathrm{NiCN}_{4}\right]^{2-}\) are diamagnetic and \(\left[\mathrm{Ni}(\mathrm{Cl})_{4}\right]^{2-}\) is paramagnetic (d) \(\left[\mathrm{Ni}(\mathrm{CO})_{4}\right]\) is diamagnetic and \(\left[\mathrm{NiCl}_{4}\right]^{2}\) and \(\left[\mathrm{Ni}(\mathrm{CN})_{4}\right]^{2-}\) are paramagnetic
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