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Buta-1,3-diene (simply called butadiene thereafter) is a diene of chemical formula C4H6, which was iPhysical Chemistry — Electrochemistry Chemistry Question

Butadiene π-electron system

Buta-1,3-diene (simply called butadiene thereafter) is a diene of chemical formula C4H6, which was isolated for the first time in 1863 by the French chemist E. Caventou and identified in 1886 by the English chemist H. E. Armstrong. It is a key reagent in the... 𝛹3 = 0.6015 𝜑1 − 0.3717 𝜑2 − 0.3717 𝜑3 + 0.6015 𝜑4 ; E3 = α − 0.62 β 𝛹4 = 0.3717 𝜑1 − 0.6015 𝜑2 + 0.6015 𝜑3 − 0.3717 𝜑4 ; E4 = α − 1.62 β
We consider the formation of the butadiene π-electron system, starting from four...

1.1.

Question text missing in source.

Model Answer

Butadiene possesses 4 π-electrons.

1.2.

Draw and fill in the MO diagram of butadiene. Draw schematically each MO and identify its nature (bonding or anti-bonding).

1.3.

Question text missing in source.

Model Answer

ΔEf = 2 E1 + 2 E2 – 4 α = 4.48 β

1.4.

Question text missing in source.

Model Answer

ΔEc = 2 E1 + 2 E2 – 2 × 2(α + β) = 0.48 β < 0
Correct statement: Butadiene

1.5.

Question text missing in source.

Model Answer

q1 = q2 = 0; q3 = q2 = 0 and q1 = q4 = 0

1.6.

Question text missing in source.

Model Answer

I12 = 0.8943; I23 = 0.4473; I34 = 0.8943
Strongest double-bond character: bonds C1C2 and C3C4.

1.7.

Question text missing in source.

1.8.

Fill in the MO diagram of cyclobutadiene.

1.9.

Using the provided diagram and considering the symmetry of the molecule, determine the missing coefficients (cij) in the following MO expressions.
𝛹1 = 0.500 𝜑1 + c12 𝜑2 + c13 𝜑3 + c14 𝜑4
𝛹2 = 0.707 𝜑1 + c22 𝜑2 + c23 𝜑3 + c24 𝜑4
𝛹3 = c31𝜑1 + 0.707 𝜑2 + c33 𝜑3 + c34 𝜑4
𝛹4 = 0.500 𝜑1 + c42 𝜑2 + c43 𝜑3 + c44 𝜑4

Model Answer

c12 = c13 = c14 = 0.5
c22 = c24 = 0; c23 = –0.707
c31 = c33 = 0; c34 = –0.707
c42 = c44 = –0.5; c43 = 0.5

1.10.

Calculate the formation and conjugation energies, ΔEf’ and ΔEc’, for cyclobutadiene.

Model Answer

ΔEf’ = 2 E1 + 2 E2 – 4 α = 4 β
ΔEc’ = 2 E1 + 2 E2 – 2 × 2(α + β) = 0
Correct answer: Both are equally stable

1.11.

Question text missing in source.

Model Answer

ΔEf (butadiene) < ΔEf’(cyclobutadiene)
Correct statement: Butadiene

1.12.

Question text missing in source.

Model Answer

Correct statements:
This deformation stabilizes C=C double bonds. (shortening of the double bonds,

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