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P Block Elements question

2017 · Shift 2 · Q10
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P Block Elements question

2017 · Shift 2 · Q10

JEE AdvancedChemistryP Block ElementsMultiple correct+4 / −1
Among the following, the correct statement(s) is (are)
  1. A
    Al(CH3)3Al{\left( {C{H_3}} \right)_3}Al(CH3​)3​ has the three-centre two-electron bonds in its dimeric structure
  2. B
    BH3B{H_3}BH3​ has the three-center two-electron bonds in its dimeric structure
  3. C
    AlCl3AlC{l_3}AlCl3​ has the three-center two-electron bonds in its dimeric structure
  4. D
    The Lewis acidity of BCl3BC{l_3}BCl3​ is greater than that of AlCl3AlC{l_3}AlCl3​
View written solutionFree

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: Al(CH3)3Al{\left( {C{H_3}} \right)_3}Al(CH3​)3​ has the three-centre two-electron bonds in its dimeric structure.

  1. Trimethylaluminium, Al(CH3)3Al(CH_3)_3Al(CH3​)3​, is an electron-deficient molecule because the central Aluminium atom has only 6 electrons in its valence shell.
  2. To achieve stability, it dimerizes to form Al2(CH3)6Al_2(CH_3)_6Al2​(CH3​)6​.
  3. In the dimeric structure, there are four terminal methyl groups (forming normal 2-centre 2-electron bonds) and two bridging methyl groups.
  4. 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.
  5. 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.
  6. Therefore, the statement is correct.

Step 2: Analyze statement B

Statement B: BH3B{H_3}BH3​ has the three-center two-electron bonds in its dimeric structure.

  1. Borane, BH3BH_3BH3​, is also an electron-deficient molecule as Boron has only 6 valence electrons.
  2. It exists as a dimer, diborane (B2H6B_2H_6B2​H6​).
  3. The structure of diborane has four terminal hydrogen atoms (in one plane) and two bridging hydrogen atoms (one above and one below the plane).
  4. The terminal B-H bonds are normal 2-centre 2-electron (2c-2e) covalent bonds.
  5. 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).
  6. Therefore, the statement is correct.

Step 3: Analyze statement C

Statement C: AlCl3AlC{l_3}AlCl3​ has the three-center two-electron bonds in its dimeric structure.

  1. Aluminium trichloride, AlCl3AlCl_3AlCl3​, is electron-deficient and dimerizes in the vapor phase to form Al2Cl6Al_2Cl_6Al2​Cl6​.
  2. The structure of the dimer is similar to that of Al2(CH3)6Al_2(CH_3)_6Al2​(CH3​)6​ with two bridging chlorine atoms and four terminal chlorine atoms.
  3. 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.
  4. Let's consider the Al−Cl−AlAl-Cl-AlAl−Cl−Al 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.
  5. 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 BCl3BC{l_3}BCl3​ is greater than that of AlCl3AlC{l_3}AlCl3​.

  1. Lewis acids are electron-pair acceptors. Both BCl3BCl_3BCl3​ and AlCl3AlCl_3AlCl3​ are Lewis acids because the central atoms (B and Al) have an incomplete octet and an empty p-orbital.
  2. Several factors influence Lewis acidity. In BCl3BCl_3BCl3​, there is pπ−pπp\pi - p\pipπ−pπ 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.
  3. In AlCl3AlCl_3AlCl3​, back-bonding between the 3p-orbital of Al and the 3p-orbital of Cl (3pπ−3pπ3p\pi - 3p\pi3pπ−3pπ) is very weak and ineffective due to the larger size of the orbitals and greater energy difference.
  4. Based on back-bonding alone, AlCl3AlCl_3AlCl3​ should be a stronger Lewis acid. However, other factors like electronegativity and the energy released upon adduct formation must be considered.
  5. Boron is significantly more electronegative than Aluminium (Pauling scale: B ≈ 2.04, Al ≈ 1.61). This makes the Boron atom in BCl3BCl_3BCl3​ more electron-deficient and a better electron-pair acceptor than Aluminium in AlCl3AlCl_3AlCl3​.
  6. Experimental data, such as the enthalpy of formation of adducts with Lewis bases (e.g., pyridine), shows that BCl3BCl_3BCl3​ forms more stable adducts than AlCl3AlCl_3AlCl3​. This confirms that BCl3BCl_3BCl3​ is a stronger Lewis acid than AlCl3AlCl_3AlCl3​. The effect of higher electronegativity and smaller size of Boron outweighs the effect of back-bonding in this case.
  7. 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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