The metal-carbon bonds in metal carbonyls have both \(ÃÆ’\) and \(À\)characters. A \(ÃÆ’\) bond is formed when the carbonyl carbon donates a lone pair of electrons to the vacant orbital of the metal. A \(À\) bond is formed by the donation of a pair of electrons from the filled metal d orbital into the vacant anti-bonding \(À*\) orbital (also known as back bonding of the carbonyl group). The \(ÃÆ’\) bond strengthens the \(À\) bond and vice-versa. Thus, a synergic effect is created due to this metal-ligand bonding. This synergic effect strengthens the bond between CO and the metal.
Write IUPAC names of the following compounds and classify them into primary, secondary and tertiary amines.
(i) (CH3 )2CHNH2 (ii) CH3 (CH2 )2NH2 (iii) CH3NHCH(CH3 )2
(iv) (CH3 )3CNH2 (v) C6H5NHCH3 (vi) (CH3CH2 )2NCH3 (vii) m–BrC6H4NH2
Give one chemical test to distinguish between the following pairs of compounds.
(i) Methylamine and dimethylamine
(ii) Secondary and tertiary amines
(iii) Ethylamine and aniline
(iv) Aniline and benzylamine
(v) Aniline and N-methylaniline
Account for the following:
(i) pKb of aniline is more than that of methylamine.
(ii) Ethylamine is soluble in water whereas aniline is not.
(iii) Methylamine in water reacts with ferric chloride to precipitate hydrated ferric oxide.
(iv) Although amino group is o– and p– directing in aromatic electrophilic substitution reactions, aniline on nitration gives a substantial amount of m-nitroaniline.
(v) Aniline does not undergo Friedel-Crafts reaction.
(vi) Diazonium salts of aromatic amines are more stable than those of aliphatic amines. (vii) Gabriel phthalimide synthesis is preferred for synthesising primary amines.
\(FeSO_4\) solution mixed with\( (NH_4)_2SO_4 \) solution in\( 1:1\) molar ratio gives the test of \(Fe^{2+}\) ion but \(CuSO_4\) solution mixed with aqueous ammonia in \( 1:4 \) molar ratio does not give the test of \(Cu^{2+}\) ion. Explain why?
Specify the oxidation numbers of the metals in the following coordination entities:
(i)\( [Co(H_2O)(CN)(en)_2] ^{2+}\)
(ii) \([CoBr_2(en)_2]^{+}\)
(iii)\( [PtCl_4]^{ 2–} \)
(iv) \(K_3[Fe(CN)_6]\)
(v) \([Cr(NH_3)_3Cl_3] \)
The metal-carbon bond possesses both the σ and π character in a metal carbonyl. The synergic effect produced by the metal-ligand bond strengthens the bond between the carbonyl molecule and the metal. The types of bonding that exist in metal carbonyls are as follows:
They are found to dissociate in various solutions. The stability of a coordination compound in a solution mainly depends on the degree of association between the two species involved in the state of equilibrium. For the formation of the compound quantitatively the stability of any complex is given by the magnitude of the equilibrium constant. For instance,
A + 4B→ AB4