$$SC{N^ - }$$ is a monodentate ligand hence cannot show chelation.
192.
Ammonia forms the complex ion $${\left[ {Cu{{\left( {N{H_3}} \right)}_4}} \right]^{2 + }}$$ with copper ions in alkaline solutions but not in acidic solutions. What is the reason for it?
A
In acidic solutions protons coordinate with ammonia molecules forming $$NH_4^ + $$ ions and $$N{H_3}$$ molecules are not available
B
In alkaline solutions insoluble $$Cu{\left( {OH} \right)_2}$$ is precipitated which is soluble in excess of any alkali
C
Copper hydroxide is an amphoteric substance
D
In acidic solutions hydration protects copper ions
Answer :
In acidic solutions protons coordinate with ammonia molecules forming $$NH_4^ + $$ ions and $$N{H_3}$$ molecules are not available
Key concept Wavelength $$\left( \lambda \right)$$ of absorption is inversely proportional to $$CFSE$$ $$\left( {{\vartriangle _o}\,{\text{value}}} \right)$$ of ligands attached with the central metal ion
$${\text{i}}{\text{.e}}{\text{.}}\,\,\lambda \propto \frac{1}{{{\Delta _O}}}$$
According to spectrochemical series.
$${I^ - } < B{r^ - } < {S^{2 - }} < SC{N^ - }$$ $$ < C{l^ - } < {F^ - } < O{H^ - } < {C_2}O_4^{2 - }$$ $$ < {O^{2 - }} < {H_2}O < NS{S^ - } < N{H_3}$$ $$ < en < NO_2^ - < C{N^ - }$$
The $$CFSE$$ of ligands attached with $$C{O^{3 + }}$$ $$ion$$ is in the order $$en > N{H_3} > {H_2}O$$ ( From spectrochemical series )
$$\because $$ Wavelength of absorbed light $$\left( \lambda \right) \propto \frac{1}{{{\vartriangle _o}}}$$
$$\therefore $$ For ligand the order of wavelength of absorption in
the visible region will be : $$en < N{H_3} < {H_2}O$$
$${\text{or,}}{\left[ {Co{{\left( {en} \right)}_3}} \right]^{3 + }} < {\left[ {Co{{\left( {N{H_3}} \right)}_6}} \right]^{3 + }}$$ $$ < {\left[ {Co{{\left( {{H_2}O} \right)}_6}} \right]^{3 + }}$$
194.
$$M{n^{2 + }}$$ forms a complex with $$B{r^ - }\,ion.$$ The magnetic moment of the complex is $$5.92\,B.M.$$ What would be the probable formula and geometry of the complex ?
A
$${\left[ {MnB{r_6}} \right]^{4 - }},{\text{octahedral}}$$
B
$${\left[ {MnB{r_4}} \right]^{2 - }},{\text{square planar}}$$
C
$${\left[ {MnB{r_4}} \right]^{2 - }},{\text{tetrahedral}}$$
D
$${\left[ {MnB{r_5}} \right]^{3 - }},{\text{trigonal bipyramidal}}$$
The number of geometrical isomers
$$\eqalign{
& {\left[ {Co{{\left( {N{H_3}} \right)}_2}{{\left( {Cl} \right)}_4}} \right]^ - } - 2 \cr
& AuC{l_2}B{r_2} - 2 \cr} $$
$${\left[ {Co\left( {N{O_2}} \right){{\left( {N{H_3}} \right)}_5}} \right]^{2 + }} - $$ No isomerism
197.
Which of the following statements is correct for the complex $$C{a_2}\left[ {Fe{{\left( {CN} \right)}_5}{O_2}} \right]$$ having $${t_{2g}}^6,{e_g}^0$$ electronic configuration ?
A
$${d^2}s{p^3}$$ hybridised and diamagnetic
B
$$s{p^3}{d^2}$$ hybridised and paramagnetic
C
$$s{p^3}{d^2}$$ hybridised and diamagnetic
D
$${d^2}s{p^3}$$ hybridised and paramagnetic
Answer :
$${d^2}s{p^3}$$ hybridised and paramagnetic
Complex is paramagnetic due to presence of unpaired electron at $$O_2^ - $$ i.e., superoxide acting as ligand.
198.
$$NiC{l_2}\,{\left\{ {P{{\left( {{C_2}{H_5}} \right)}_2}\left( {{C_6}{H_5}} \right)} \right\}_2}$$ exhibits temperature depend-ent magnetic behaviour (paramagnetic/diamagnetic). The coordination geometries of $$N{i^{2 + }}$$ in the paramagnetic and diamagnetic states are respectively.
In both states (paramagnetic and diamagnetic) of the given complex, $$Ni$$ exists as $$N{i^{2 + }}$$ whose electronic configuration is $$\left[ {Ar} \right]3{d^8}4{s^0}.$$
In the above paramagnetic state the geometry of the complex is $$s{p^3}$$ giving tetrahedral geometry. The diamagnetic state is achieved by pairing of electrons in $$3d$$ orbital.
Thus the geometry of the complex will be $$ds{p^2}$$ giving square planar geometry.
In $$Fe{\left( {CO} \right)_5},$$ $$Fe$$ - atom is in $$ds{p^3}$$ hybridised state, therefore the shape of molecule is trigonal bipyramidal. The hybridisation is as follows :
$$_{26}Fe = 1{s^2},2{s^2}2{p^6},3{s^2}3{p^6}3{d^6},4{s^2}4{p^0}$$
In presence of strong field ligand $$(CO),$$ the electrons of $$4s$$ are pushed in $$3d$$ orbital and get paired up.
In $$Fe{\left( {CO} \right)_5},$$ the $$Fe$$ - atom is
200.
Which of the following statements related to crystal field splitting in octahedral coordination entities is incorrect ?
A
The $$d{x^2} - {y^2}$$ and $$d{z^2}$$ orbitals has more energy as compared to $${d_{xy}},{d_{yz}}$$ and $${d_{xz}}$$ orbitals.
B
Crystal field splitting energy $$\left( {{\Delta _ \circ }} \right)$$ depends directly on the charge of the metal ion and on the field produced by the ligand.
C
In the presence of $$B{r^ - }$$ as a ligand the distribution of electrons for $${d^4}$$ configuration will be $$t_{{2_g}}^3,e_g^1,$$
D
In the presence of $$C{N^ - }$$ as a ligand $${\Delta _ \circ } < P.$$
Answer :
In the presence of $$C{N^ - }$$ as a ligand $${\Delta _ \circ } < P.$$