JEE AdvancedChemistryP Block ElementsMultiple correct+4 / −1
Among the following, the correct statement(s) is (are)
- Ahas the three-centre two-electron bonds in its dimeric structure
- Bhas the three-center two-electron bonds in its dimeric structure
- Chas the three-center two-electron bonds in its dimeric structure
- DThe Lewis acidity of is greater than that of
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Correct answer: A, B, D
This question assesses the understanding of bonding in electron-deficient compounds of Boron and Aluminium (Group 13) and their Lewis acidity.
Step 1: Analyze statement A
Statement A: has the three-centre two-electron bonds in its dimeric structure.
- Trimethylaluminium, , is an electron-deficient molecule because the central Aluminium atom has only 6 electrons in its valence shell.
- To achieve stability, it dimerizes to form .
- In the dimeric structure, there are four terminal methyl groups (forming normal 2-centre 2-electron bonds) and two bridging methyl groups.
- Each bridging methyl group is bonded to two Aluminium atoms. An sp³ orbital from the bridging carbon atom overlaps simultaneously with sp³ orbitals from the two Aluminium atoms.
- This forms a three-centre bond (Al-C-Al). The bond is formed by sharing a single pair of electrons among these three atoms. This type of bond is known as a three-centre two-electron (3c-2e) bond.
- Therefore, the statement is correct.
Step 2: Analyze statement B
Statement B: has the three-center two-electron bonds in its dimeric structure.
- Borane, , is also an electron-deficient molecule as Boron has only 6 valence electrons.
- It exists as a dimer, diborane ().
- The structure of diborane has four terminal hydrogen atoms (in one plane) and two bridging hydrogen atoms (one above and one below the plane).
- The terminal B-H bonds are normal 2-centre 2-electron (2c-2e) covalent bonds.
- The bridging B-H-B bonds are three-centre two-electron (3c-2e) bonds. In these bonds, a single pair of electrons binds the three atoms (two Boron and one Hydrogen).
- Therefore, the statement is correct.
Step 3: Analyze statement C
Statement C: has the three-center two-electron bonds in its dimeric structure.
- Aluminium trichloride, , is electron-deficient and dimerizes in the vapor phase to form .
- The structure of the dimer is similar to that of with two bridging chlorine atoms and four terminal chlorine atoms.
- However, the bonding in the bridge is different. Each bridging chlorine atom has lone pairs of electrons. It forms a normal covalent bond with one Aluminium atom and uses one of its lone pairs to form a coordinate (dative) bond with the other electron-deficient Aluminium atom.
- Let's consider the bridge. It involves a 2-centre 2-electron covalent bond and a 2-centre 2-electron coordinate bond. In total, there are four electrons involved in the three-centre bridge. This is described as a three-centre four-electron (3c-4e) bond system.
- Since the bond is a 3c-4e type, not 3c-2e, the statement is incorrect.
Step 4: Analyze statement D
Statement D: The Lewis acidity of is greater than that of .
- Lewis acids are electron-pair acceptors. Both and are Lewis acids because the central atoms (B and Al) have an incomplete octet and an empty p-orbital.
- Several factors influence Lewis acidity. In , there is back-bonding between the filled p-orbitals of chlorine and the empty 2p-orbital of boron. This delocalization of electrons reduces the electron deficiency on the boron atom, thereby decreasing its Lewis acidity.
- In , back-bonding between the 3p-orbital of Al and the 3p-orbital of Cl () is very weak and ineffective due to the larger size of the orbitals and greater energy difference.
- Based on back-bonding alone, should be a stronger Lewis acid. However, other factors like electronegativity and the energy released upon adduct formation must be considered.
- Boron is significantly more electronegative than Aluminium (Pauling scale: B ≈ 2.04, Al ≈ 1.61). This makes the Boron atom in more electron-deficient and a better electron-pair acceptor than Aluminium in .
- Experimental data, such as the enthalpy of formation of adducts with Lewis bases (e.g., pyridine), shows that forms more stable adducts than . This confirms that is a stronger Lewis acid than . The effect of higher electronegativity and smaller size of Boron outweighs the effect of back-bonding in this case.
- Therefore, the statement is correct.
Conclusion
Based on the analysis, statements A, B, and D are correct, while statement C is incorrect.
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