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Question #44337

Difficulty: 8/10 | 🟢 Free

The Question

In transition metal coordination chemistry, thermodynamic stability is classically predicted by Fajans' rules, where a higher central cation charge enhances electrostatic polarization and metal-ligand attraction. However, for π\pi-acceptor ligands, synergic orbital-overlap often dictates stability. Consider the isoelectronic octahedral complexes \ce{[V(CO)6]^-} (I), \ce{Cr(CO)6} (II), and \ce{[Mn(CO)6]^+} (III). Let xx, yy, and zz represent their respective \ce{C-O} stretching frequencies (ν\ceCO\nu_{\ce{CO}}). Furthermore, let y′y' be the average ν\ceCO\nu_{\ce{CO}} of the remaining carbonyl ligands when one \ce{CO} in \ce{Cr(CO)6} is substituted by \ce{PMe3} (trimethylphosphine). Which of the following correctly establishes the relationship between these frequencies, demonstrating the dominance of synergic back-bonding over simple electrostatic polarization?

Options

  • A.

    x<y<zx < y < z and y′<yy' < y

  • B.

    x<y<zx < y < z and y′>yy' > y

  • C.

    x>y>zx > y > z and y′<yy' < y

  • D.

    x>y>zx > y > z and y′>yy' > y

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Correct Answer

Step-by-Step Solution

Explanation

How the Examiner Thinks

Exception_Exposure

Learn to identify edge cases and boundary exceptions that JEE examiners hide in math problems.

Concepts Behind This Question

Fajans' Rule Polarization Power|Synergic Bonding in Carbonyls|d-block Variable Oxidation States

Why This Question Is Tricky

Common Mistakes

The question tests the 'Chemical Exception' where classical electrostatic rules (Fajans' rules) fail to predict the bonding nature of transition metal complexes with pi-acceptor ligands.

Students often mistakenly apply electrostatic polarization (favoring high cation charge) to predict bond strengths, overlooking that in metal carbonyls, the dominant force is synergic back-bonding, which requires electron-rich metals in low/negative oxidation states.

Furthermore, it tests the 'Hidden Variable' of spectator ligand effects, where substituting a pi-acid (CO) with a sigma-donor (PMe3) forces the metal to redistribute its increased electron density, thereby strengthening the back-bonding to the remaining CO ligands and lowering their stretching frequency.

Quick Facts About This Question

Question Information

SubjectChemistry
ChapterChemical Bonding and Molecular Structure - Class 11 Part 1
ConceptFajans' Rule Polarization Power
Difficulty8
Cognitive Load7
Target Solve Time160 sec
AccessFree