101. Six monodentate ligands around a metal are replaced by two tridentate ligands. The most accurate comparison is:
ⓐ. ligand count falls from \(6\) to \(2\), while coordination number remains \(6\)
ⓑ. ligand-particle count and coordination number both decrease from \(6\) to \(2\)
ⓒ. ligand-particle count remains \(6\), while coordination number becomes \(2\)
ⓓ. coordination number increases from \(6\) to \(12\)
Correct Answer: ligand count falls from \(6\) to \(2\), while coordination number remains \(6\)
Explanation: Each monodentate ligand contributes one donor atom, so six such ligands give coordination number \(6\). Each tridentate ligand contributes three donor atoms. Two tridentate ligands therefore also provide \(2\times3=6\) metal–donor attachments. The number of ligand particles falls from six to two even though the coordination number is unchanged. This reduction in bound ligand count can accompany release of several separate particles during chelate formation.
102. Study the proposed stability factors.
| Row | Factor | Expected influence |
| P | Multiple donor attachments from one ligand | Can favour retention of the ligand |
| Q | Severe mismatch between donor spacing and metal size | Always increases stability |
| R | Formation of suitably sized chelate rings | Can favour complex stability |
| S | Release of several monodentate ligands | Can give a favourable entropy contribution |
The supported rows are:
ⓐ. P and Q only
ⓑ. Q and R only
ⓒ. P, R and S
ⓓ. P, Q, R and S
Correct Answer: P, R and S
Explanation: Multiple attachment points can make complete ligand separation less probable, so Row P is supported. Suitably sized rings can form without excessive strain and may contribute to stable chelation, supporting Row R. Release of several separate ligands can increase the number of free particles and favour the process entropically, supporting Row S. Row Q is unsuitable because poor donor spacing can introduce strain or prevent effective simultaneous bonding. Structural compatibility matters as much as the mere presence of several donor atoms.
103. The claim “chelating ligands always form more stable complexes than monodentate ligands” requires modification because:
ⓐ. chelating ligands never form metal–ligand bonds
ⓑ. ring strain or poor fit can offset chelate stability
ⓒ. monodentate ligands always have greater denticity
ⓓ. entropy never contributes to coordination equilibria
Correct Answer: ring strain or poor fit can offset chelate stability
Explanation: The chelate effect is a strong general trend, but it depends on a suitable geometric and electronic match. If donor atoms are too close together or too far apart, simultaneous binding may strain the ligand or distort the metal environment. An unsuitable donor type may also interact weakly with a particular metal ion. Very small or very large rings can be less favourable than rings of appropriate size. Stability comparisons therefore require comparable bonding conditions rather than an absolute rule based only on denticity.
104. A metal complex \(\mathrm{[ML_6]}\) is converted completely into \(\mathrm{[M(en)_3]}\). If \(0.50\,\mathrm{mol}\) of \(\mathrm{[ML_6]}\) reacts according to
\[
\mathrm{[ML_6]+3en\rightarrow[M(en)_3]+6L},
\]
the total moles of free \(L\) released and \(\mathrm{en}\) consumed are respectively:
ⓐ. \(3.0\,\mathrm{mol}\) and \(1.5\,\mathrm{mol}\)
ⓑ. \(1.5\,\mathrm{mol}\) and \(3.0\,\mathrm{mol}\)
ⓒ. \(6.0\,\mathrm{mol}\) and \(3.0\,\mathrm{mol}\)
ⓓ. \(3.0\,\mathrm{mol}\) and \(0.50\,\mathrm{mol}\)
Correct Answer: \(3.0\,\mathrm{mol}\) and \(1.5\,\mathrm{mol}\)
Explanation: \( \textbf{Reaction amount:} \) The starting complex is present in an amount of \(0.50\,\mathrm{mol}\).
\( \textbf{Ligand-release ratio:} \)
\[
1\,\mathrm{mol}\,\mathrm{[ML_6]}\rightarrow6\,\mathrm{mol}\ L
\]
\( \textbf{Free }L\textbf{ released:} \)
\[
0.50\times6=3.0\,\mathrm{mol}
\]
\( \textbf{Chelating-ligand ratio:} \)
\[
1\,\mathrm{mol}\,\mathrm{[ML_6]}\text{ consumes }3\,\mathrm{mol}\,\mathrm{en}
\]
\( \textbf{Amount of } \mathrm{en}\textbf{ consumed:} \)
\[
0.50\times3=1.5\,\mathrm{mol}
\]
\( \textbf{Coordination-number check:} \) Six monodentate donor atoms are replaced by six nitrogen donor atoms from three \(\mathrm{en}\) ligands.
\( \textbf{Particle interpretation:} \) More separate \(L\) particles are released than \(\mathrm{en}\) particles consumed.
\( \textbf{Final answer:} \) The process releases \(3.0\,\mathrm{mol}\) of \(L\) and consumes \(1.5\,\mathrm{mol}\) of \(\mathrm{en}\).
105. Use the two arrangements described below.
Case 1: One \(\mathrm{Cl^-}\) ligand is bonded to two metal centres.
Case 2: One \(\mathrm{en}\) ligand uses both nitrogen atoms to bind the same metal centre.
The ligand roles in Case 1 and Case 2 are respectively:
ⓐ. chelating and bridging
ⓑ. bridging and chelating
ⓒ. ambidentate and monodentate
ⓓ. bidentate and terminal
Correct Answer: bridging and chelating
Explanation: In Case 1, one chlorido ligand connects two metal centres and therefore acts as a bridging ligand. In Case 2, both nitrogen atoms of the same \(\mathrm{en}\) molecule bind one metal centre. The ligand chain and metal form a chelate ring. Bridging concerns connection between different metal centres, whereas chelation concerns multiple attachment to one metal. The two arrangements cannot be distinguished merely from ligand charge.
106. Match each description in Column I with the appropriate classification in Column II.
| Column I | Column II |
| P. One \(\mathrm{OH^-}\) joins two metal ions | 1. Terminal monodentate |
| Q. One \(\mathrm{en}\) binds one metal through two nitrogen atoms | 2. Bridging |
| R. One \(\mathrm{NH_3}\) binds one metal through nitrogen | 3. Chelating |
| S. One \(\mathrm{CO}\) connects two metal atoms | 4. Bridging carbonyl |
ⓐ. P-3, Q-2, R-4, S-1
ⓑ. P-2, Q-4, R-1, S-3
ⓒ. P-2, Q-3, R-1, S-4
ⓓ. P-4, Q-1, R-3, S-2
Correct Answer: P-2, Q-3, R-1, S-4
Explanation: A hydroxido ligand joining two metals is bridging, so P matches \(2\). Ethane-1,2-diamine binding twice to one metal forms a chelate and matches \(3\). A single ammonia ligand attached through nitrogen is terminal and monodentate, giving R-\(1\). A carbonyl ligand connecting two metal atoms is described as a bridging carbonyl, giving S-\(4\). The same broad ligand family may adopt terminal or bridging modes depending on the actual bonding arrangement.
107. Consider the following statements about bridging ligands.
Statement I: The symbol \(\mu\) is used at recognition level to indicate a bridging ligand.
Statement II: A bridging ligand can contribute a metal–ligand bond to more than one metal centre.
Statement III: Every bridging ligand must also form a chelate ring around one metal.
The valid statements are:
ⓐ. I and II only
ⓑ. II and III only
ⓒ. I and III only
ⓓ. I, II and III
Correct Answer: I and II only
Explanation: The notation \(\mu\) is commonly used to show that a ligand bridges metal centres. Such a ligand makes direct bonding interactions with more than one metal. This arrangement can produce multinuclear coordination entities. Bridging does not require the ligand to form a ring around one metal, so Statement III is invalid. A ligand may be bridging without being chelating, just as a chelating ligand may involve only one metal centre.
108. A dinuclear entity contains two metal centres. Each metal is bonded to two terminal \(\mathrm{Cl^-}\) ligands, and two additional \(\mathrm{Cl^-}\) ligands bridge both metals. The total number of metal–chlorine bonds is:
ⓐ. \(4\)
ⓑ. \(6\)
ⓒ. \(10\)
ⓓ. \(8\)
Correct Answer: \(8\)
Explanation: \( \textbf{Terminal ligands per metal:} \) Each metal has two terminal chlorido ligands.
\( \textbf{Total terminal ligands:} \)
\[
2\times2=4
\]
\( \textbf{Bonds from terminal ligands:} \) Each terminal ligand forms one metal–chlorine bond.
\[
4\times1=4
\]
\( \textbf{Number of bridging ligands:} \) Two chlorido ligands bridge the two metals.
\( \textbf{Bonds per bridge:} \) Each bridging chloride forms one bond to each metal, giving two bonds.
\[
2\times2=4
\]
\( \textbf{Total metal–chlorine bonds:} \)
\[
4+4=8
\]
\( \textbf{Final answer:} \) The entity contains \(8\) metal–chlorine bonds; counting each bridge as only one bond would miss its attachment to the second metal.
109. In a symmetrical dimer, each metal is bonded to two terminal ligands and to two ligands that bridge both metals. Assuming every bond involves one donor atom, the coordination number of each metal is:
ⓐ. \(2\)
ⓑ. \(3\)
ⓒ. \(4\)
ⓓ. \(6\)
Correct Answer: \(4\)
Explanation: \( \textbf{Terminal contribution:} \) Each metal receives two donor-atom attachments from its two terminal ligands.
\[
\mathrm{CN_{terminal}}=2
\]
\( \textbf{Bridging contribution:} \) Both bridging ligands also bond to each metal.
\[
\mathrm{CN_{bridging}}=2
\]
\( \textbf{Coordination number per metal:} \)
\[
\mathrm{CN}=2+2
\]
\[
\mathrm{CN}=4
\]
\( \textbf{Counting rule:} \) A bridging ligand is counted once for each direct donor-atom attachment to the particular metal being considered.
\( \textbf{Dimer distinction:} \) The total number of bonds in the whole dimer is larger than the coordination number of one metal.
\( \textbf{Final answer:} \) Each metal has coordination number \(4\), even though the two bridges are shared between the metal centres.
110. The coordination number of a central metal is determined by counting:
ⓐ. all atoms present in the ligands
ⓑ. the number of species written outside the square brackets
ⓒ. the total charge carried by the ligands
ⓓ. ligand donor atoms directly bonded to the metal
Correct Answer: ligand donor atoms directly bonded to the metal
Explanation: Coordination number counts the donor atoms that form direct bonds with the central metal. A monodentate ligand contributes one, a bidentate ligand contributes two, and a tridentate ligand contributes three when all stated donor sites are attached. The total number of atoms in a ligand is irrelevant to this count. Counter ions outside the brackets do not contribute because they are not directly coordinated. Ligand charge is used in oxidation-state calculations rather than in determining coordination number.
111. An entity contains one bidentate \(\mathrm{en}\) ligand, one bidentate oxalato ligand, and two monodentate \(\mathrm{NH_3}\) ligands. Its coordination number and total number of ligand particles are respectively:
ⓐ. \(4\) and \(6\)
ⓑ. \(5\) and \(4\)
ⓒ. \(6\) and \(6\)
ⓓ. \(6\) and \(4\)
Correct Answer: \(6\) and \(4\)
Explanation: One \(\mathrm{en}\) ligand contributes two nitrogen donor atoms. One oxalato ligand contributes two oxygen donor atoms. The two ammonia ligands contribute one donor atom each, giving two more attachments. The coordination number is therefore \(2+2+2=6\). The number of ligand particles is only \(1+1+2=4\), showing why ligand count and coordination number need not be equal.
112. For \(\mathrm{[Cr(NH_3)_4Cl_2]Cl}\), the oxidation state of chromium, charge on the coordination entity, and coordination number are respectively:
ⓐ. \(+2\), \(1+\), and \(4\)
ⓑ. \(+3\), \(2+\), and \(6\)
ⓒ. \(+3\), \(1+\), and \(6\)
ⓓ. \(+1\), \(1+\), and \(5\)
Correct Answer: \(+3\), \(1+\), and \(6\)
Explanation: \( \textbf{External counter ion:} \) One \(\mathrm{Cl^-}\) lies outside the brackets.
\( \textbf{Complex charge:} \) The bracketed entity must therefore carry charge \(1+\).
\( \textbf{Ligand charges:} \) Four \(\mathrm{NH_3}\) ligands are neutral, while two coordinated \(\mathrm{Cl^-}\) ligands contribute \(-2\).
\( \textbf{Let chromium oxidation state be:} \) \(x\).
\( \textbf{Charge equation:} \)
\[
x+4(0)+2(-1)=+1
\]
\( \textbf{Solve for chromium:} \)
\[
x-2=+1
\]
\[
x=+3
\]
\( \textbf{Coordination-number count:} \) All six ligands are monodentate.
\[
\mathrm{CN}=4(1)+2(1)=6
\]
\( \textbf{Final answer:} \) The values are \(+3\), \(1+\), and \(6\); oxidation state, complex charge, and coordination number arise from different calculations.
113. Consider the following statements.
Statement I: Coordination number counts directly bonded donor atoms.
Statement II: Oxidation state is obtained by algebraic charge balance.
Statement III: Coordination number must always equal the charge on the coordination entity.
Statement IV: The number of ligand particles may be smaller than the coordination number.
The valid statements are:
ⓐ. I and III only
ⓑ. I, II and IV only
ⓒ. II and III only
ⓓ. I, II, III and IV
Correct Answer: I, II and IV only
Explanation: Statement I gives the correct definition of coordination number. Statement II correctly describes oxidation-state determination from the metal, ligand charges, and net complex charge. Statement III is invalid because coordination number is a bond-counting quantity, whereas complex charge is an algebraic electrical quantity. Statement IV is valid for complexes containing multidentate ligands. In \(\mathrm{[M(en)_3]^{n+}}\), three ligand particles produce coordination number \(6\).
114. A six-coordinate entity has the formula \(\mathrm{[M(dien)(NH_3)_x]^{q}}\), where \(\mathrm{dien}\) is tridentate and every \(\mathrm{NH_3}\) is monodentate. The value of \(x\) and the total number of ligand particles are:
ⓐ. \(x=2\) and \(3\) particles
ⓑ. \(x=6\) and \(7\) particles
ⓒ. \(x=1\) and \(4\) particles
ⓓ. \(x=3\) and \(4\) particles
Correct Answer: \(x=3\) and \(4\) particles
Explanation: \( \textbf{Required coordination number:} \) The entity is six-coordinate.
\( \textbf{Contribution from } \mathrm{dien}\textbf{:} \) One tridentate ligand contributes three donor atoms.
\[
\mathrm{CN_{dien}}=3
\]
\( \textbf{Contribution required from ammonia:} \)
\[
6-3=3
\]
\( \textbf{Denticity of ammonia:} \) Each \(\mathrm{NH_3}\) is monodentate.
\( \textbf{Number of ammonia ligands:} \)
\[
x=\frac{3}{1}=3
\]
\( \textbf{Total ligand-particle count:} \)
\[
1\mathrm{\ dien}+3\mathrm{\ NH_3}=4
\]
\( \textbf{Final answer:} \) The entity contains three ammonia ligands and four ligand particles in total, while six donor atoms surround the metal.
115. Study the coordination-number assignments.
| Entity | Assigned coordination number |
| P. \(\mathrm{[Ag(NH_3)_2]^+}\) | \(2\) |
| Q. \(\mathrm{[Co(en)_3]^{3+}}\) | \(3\) |
| R. \(\mathrm{[NiCl_4]^{2-}}\) | \(4\) |
| S. \(\mathrm{[M(EDTA)]^{n-}}\) | \(6\), when \(\mathrm{EDTA^{4-}}\) is hexadentate |
The inconsistent row is:
ⓐ. P
ⓑ. R
ⓒ. Q
ⓓ. S
Correct Answer: Q
Explanation: Two monodentate ammonia ligands give coordination number \(2\) in Row P. Four monodentate chlorido ligands give coordination number \(4\) in Row R. A hexadentate \(\mathrm{EDTA^{4-}}\) ligand contributes six donor atoms, supporting Row S. In Row Q, each \(\mathrm{en}\) ligand is bidentate, so three such ligands give \(3\times2=6\), not \(3\). The incorrect assignment results from counting ligand molecules instead of donor atoms.
116. Complex \(P\) contains six monodentate ligands, complex \(Q\) contains three bidentate ligands, and complex \(R\) contains two tridentate ligands. If all donor sites are coordinated, the three complexes:
ⓐ. ligand counts \(6\), \(3\), \(2\); coordination number \(6\) throughout
ⓑ. have coordination numbers \(6\), \(3\), and \(2\), respectively
ⓒ. have equal ligand counts but different coordination numbers
ⓓ. must have identical charges and oxidation states
Correct Answer: ligand counts \(6\), \(3\), \(2\); coordination number \(6\) throughout
Explanation: Six monodentate ligands provide \(6\times1=6\) donor atoms. Three bidentate ligands provide \(3\times2=6\), and two tridentate ligands provide \(2\times3=6\). Their ligand-particle counts differ substantially, but their coordination numbers are equal. No conclusion about charge or oxidation state follows from denticity alone. Equal coordination number describes equal numbers of metal–donor attachments, not identical chemical composition.
117. A \(0.25\,\mathrm{mol}\) sample of \(\mathrm{[M(en)_3]^{n+}}\) contains how many moles of metal–nitrogen coordinate bonds, assuming each \(\mathrm{en}\) ligand is bidentate?
ⓐ. \(0.50\,\mathrm{mol}\)
ⓑ. \(0.75\,\mathrm{mol}\)
ⓒ. \(1.00\,\mathrm{mol}\)
ⓓ. \(1.50\,\mathrm{mol}\)
Correct Answer: \(1.50\,\mathrm{mol}\)
Explanation: \( \textbf{Amount of complex:} \) The sample contains \(0.25\,\mathrm{mol}\) of coordination entities.
\( \textbf{Ligands per entity:} \) Each entity contains three \(\mathrm{en}\) ligands.
\( \textbf{Denticity of } \mathrm{en}\textbf{:} \) Each ligand forms two metal–nitrogen bonds.
\( \textbf{Bonds per coordination entity:} \)
\[
3\times2=6
\]
\( \textbf{Mole relation:} \)
\[
1\,\mathrm{mol}\,\mathrm{[M(en)_3]^{n+}}\rightarrow6\,\mathrm{mol}\,\mathrm{M-N\ bonds}
\]
\( \textbf{Substitution:} \)
\[
0.25\times6=1.50
\]
\( \textbf{Bond amount:} \)
\[
n(\mathrm{M-N\ bonds})=1.50\,\mathrm{mol}
\]
\( \textbf{Final answer:} \) The sample contains \(1.50\,\mathrm{mol}\) of metal–nitrogen coordinate bonds; multiplying only by three would count ligands rather than donor attachments.
118. An octahedral entity contains two bidentate oxalato ligands and \(x\) monodentate aqua ligands. The value of \(x\) is:
ⓐ. \(2\)
ⓑ. \(1\)
ⓒ. \(4\)
ⓓ. \(6\)
Correct Answer: \(2\)
Explanation: \( \textbf{Octahedral coordination:} \) The entity has coordination number \(6\).
\( \textbf{Contribution from oxalato ligands:} \) Each oxalato ligand is bidentate.
\[
2\times2=4
\]
\( \textbf{Remaining coordination positions:} \)
\[
6-4=2
\]
\( \textbf{Contribution from aqua ligands:} \) Each \(\mathrm{H_2O}\) ligand is monodentate.
\( \textbf{Number required:} \)
\[
x=\frac{2}{1}=2
\]
\( \textbf{Resulting ligand set:} \) Two oxalato and two aqua ligands provide six donor atoms.
\( \textbf{Final answer:} \) The value of \(x\) is \(2\); four ligand particles are sufficient to occupy six octahedral coordination positions.
119. Use the arrangement described below: four donor atoms surround a metal so that all four lie in one plane, adjacent donor positions are separated by \(90^\circ\), and opposite positions by \(180^\circ\). The geometry is:
ⓐ. tetrahedral arrangement
ⓑ. square planar
ⓒ. linear arrangement
ⓓ. octahedral arrangement
Correct Answer: square planar
Explanation: A square-planar arrangement places the metal and four donor atoms in the same plane. Adjacent positions subtend angles of \(90^\circ\), while opposite positions subtend \(180^\circ\). A tetrahedral arrangement also has coordination number \(4\), but its donor atoms do not all lie in one plane. Linear geometry contains only two donor positions. Octahedral geometry contains six positions, including two perpendicular to the square plane.
120. The different geometries of \(\mathrm{[NiCl_4]^{2-}}\) and \(\mathrm{[Ni(CN)_4]^{2-}}\), despite both having coordination number \(4\), are respectively:
ⓐ. square planar and tetrahedral
ⓑ. tetrahedral and square planar
ⓒ. linear and square planar
ⓓ. octahedral and tetrahedral
Correct Answer: tetrahedral and square planar
Explanation: \(\mathrm{[NiCl_4]^{2-}}\) is tetrahedral in the usual coordination-chemistry model. Chlorido is a weak-field ligand and does not produce the pairing associated with the square-planar arrangement in this case. The cyanido ligand is strong-field, and \(\mathrm{[Ni(CN)_4]^{2-}}\) is square planar. Both entities have four directly bonded donor atoms. Their contrast shows that coordination number must be combined with metal configuration and ligand-field effects when predicting geometry.