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Exercise · Q3

Q.The thiocyanate ion (SCN−\text{SCN}^-) and the nitrite ion (NO2−\text{NO}_2^-) are both described as ambidentate ligands. Explain what this term means, and write the two different ways each of these ions can coordinate to a metal ion, naming both linkage forms.

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An ambidentate ligand is one that possesses two (or more) different potential donor atoms, so that it can coordinate to a metal ion through either atom, giving two distinct linkage isomers (Section 5.15) depending on which one actually bonds. The thiocyanate ion, S=C=N−\text{S=C=N}^-, has both a sulfur atom and a nitrogen atom capable of donating a lone pair: when it binds through sulfur it is named thiocyanato (formula written M-SCN\text{M-SCN}), and when it binds through nitrogen it is named isothiocyanato (formula written M-NCS\text{M-NCS}). The nitrite ion, NO2−\text{NO}_2^-, similarly has both a nitrogen atom and an oxygen atom available: when it binds through nitrogen it is named nitro (formula M-NO2\text{M-NO}_2), and when it binds through one of its oxygen atoms it is named nitrito (formula M-ONO\text{M-ONO}). In both cases, the two coordination modes give chemically and structurally distinct complexes (different bond lengths, different stability, sometimes different colour), even though the free ligand itself is a single, well-defined ion. [!ANSWER] SCN−\text{SCN}^- is ambidentate: S-bonded = thiocyanato (M-SCN\text{M-SCN}), N-bonded = isothiocyanato (M-NCS\text{M-NCS}). NO2−\text{NO}_2^- is ambidentate: N-bonded = nitro (M-NO2\text{M-NO}_2), O-bonded = nitrito (M-ONO\text{M-ONO}).

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