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Question #44603

Difficulty: 8/10 | 🟢 Free

The Question

The C-O bond in free carbon monoxide gas (\ceCO(g)\ce{CO_{(g)}}) at 298 K298\text{ K} exhibits a stretching force constant of 18.6 mdyn/A˚18.6\text{ mdyn/\AA}. Consider the isoelectronic series of octahedral metal carbonyl complexes: \ce[V(CO)6]−\ce{[V(CO)_6]^-}, \ce[Cr(CO)6]\ce{[Cr(CO)_6]}, and \ce[Mn(CO)6]+\ce{[Mn(CO)_6]^+}, analyzed via IR spectroscopy in \ceCH2Cl2\ce{CH_2Cl_2} solution at 298 K298\text{ K}. The synergic bonding mechanism (M(dπ)→CO(π∗)M(d\pi) \rightarrow CO(\pi^*)) significantly alters the C-O bond strength. Which of the following sets correctly represents the C-O stretching force constants for \ce[V(CO)6]−\ce{[V(CO)_6]^-}, \ce[Cr(CO)6]\ce{[Cr(CO)_6]}, and \ce[Mn(CO)6]+\ce{[Mn(CO)_6]^+}, respectively?

Options

  • A.

    14.0,16.3,17.3 mdyn/A˚14.0, 16.3, 17.3 \text{ mdyn/\AA}

  • B.

    17.3,16.3,14.0 mdyn/A˚17.3, 16.3, 14.0 \text{ mdyn/\AA}

  • C.

    19.2,18.6,17.3 mdyn/A˚19.2, 18.6, 17.3 \text{ mdyn/\AA}

  • D.

    14.0,18.6,20.1 mdyn/A˚14.0, 18.6, 20.1 \text{ mdyn/\AA}

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Correct Answer

Step-by-Step Solution

Explanation

How the Examiner Thinks

Mechanism_Trap

Don't get tricked by the process! Learn the mechanical traps used in competitive exam questions.

Concepts Behind This Question

Synergic Bonding in Carbonyls|Oxidation State Traps

Why This Question Is Tricky

Common Mistakes

The question tests the 'Oxidation State Trap' within the context of Synergic Bonding.

Students often erroneously assume that a higher positive charge on the central metal strengthens all metal-ligand interactions uniformly.

However, for π\pi-acid ligands like \ceCO\ce{CO}, a higher positive oxidation state increases the effective nuclear charge (ZeffZ_{eff}), which contracts the metal dd-orbitals.

This 'hidden variable' drastically reduces the metal's ability to back-donate electron density into the \ceCO\ce{CO} π∗\pi^* antibonding orbital.

Consequently, textbook learners miss this electronic competition and fail to predict the 'anomalous' strengthening of the C-O bond (higher force constant) in positively charged complexes.

Quick Facts About This Question

Question Information

SubjectChemistry
ChapterCoordination Compounds - Class 12
ConceptSynergic Bonding in Carbonyls
Difficulty8
Cognitive Load7
Target Solve Time160 sec
AccessFree