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Q.

Which of the following statements is not correct?

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a

NF3 is less basic than NH3

b

 Guanidine, HN=CNH22, is a weak base. 

c

The decreasing base strength of the amines CH3CH22NH2,CH2=CHCH2NH2 and HCCH2NH2 is CH3CH22NH2>H2CCHCH2NH2>HCCCH2NH2.

d

 The bond angle in NH3 is greater than in NF3

answer is B.

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Detailed Solution

(a) In NF3 , nitrogen acquires δ+ charge because it is less electronegative than fluorine. With positive charge on nitrogen, the lone pair of electrons are more tightly held in NF3.

(b) In guanidine, the imino (=NH) nitrogen is sp2hybridised while amino (-NH2 ) is sp3 hybridised. The proton is likely to be attached to -NH2 as its nitrogen has less s-character, Actually the imino nitrogen is protonated because this leads to the stable symmetrical resonating cation with very high delocalisation energy as there are three contributing structures.

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Because of the large delocalisation energy, the cation is very much stabilised leading the guanidine to act as a strong base.

(c) Ammonia involves more bonding pair-bonding pair electronic repulsion as the pairs are located near the nitrogen atom due to its more electronegative character. In NF3, F is more electronegative and thus bonding pair lies more near F leading to less electronic repulsion.

( d) The larger the s-character of a hybrid orbital of carbon, the larger electron-withdrawing (by induction) effect it has, consequently, the larger is its base-weakening effect.

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