IC_Tutorial 1 II_Semester_2022-2023

Department of Chemistry, IIT Delhi, New Delhi

INORGANIC TUTORIAL 1; The 18-Electron Rule

1. Following the neutral atom counting method, indicate the electron count for the
following bridging ligands.
(i) 2-CO, (ii) 3-CO, (iii) 2-Cl, (iv) 3-Cl, and (v) 2-Me

2. [M(3-C5H5)(CO)5] is a stable compound; given that M is a first-row transition

element, predict M.

3. Determine the nature of the metal-metal bond in the following complexes that obey
the 18-electron rule.
(i) (CO)2Rh(-Cl)2Rh(CO)2, (ii) (5-Cp)(CO)Fe(-CO)2Fe(CO)(5-Cp), and (iii) (5-
Cp)(CO)Mo(-CO)2Mo(CO)(5-Cp)

4. Among the following three anions, which one will be formed readily?
(i) [V(CO)6], (ii) [Cr(CO)6], and (iii) [Mo(CO)6]

5. The given cationic/anionic complexes (A-D) obey the 18-electron rule. The
complex(es) having 2+ overall charge is(are),

6. The reaction of [5-CpRu(6-naphthalene)]+BF4 with (Bu4N)Br resulted in a stable

complex A having four 5-CpRuBr units. Naphthalene and (Bu4N)BF4 were the side
products of the reaction. Choose the correct structure of compound A.

7. The ligand that will make Mo(=NAr)(=CHR)(OR’)2 (with a linear Mo=N-Ar moiety)
stable is, [Ar = 2,6-(i-Pr)2C6H3, R = C(Ph)(Me)2 and R’ = C(CH3)(CF3)2]
(i) bipyridine (ii) 6C6H6 (iii) pyridine (iv) (8C8H8)2

INDIAN INSTITUTE OF TECHNOLOGY DELHI, NEW DELHI-110016

IC_Tutorial 1 II_Semester_2022-2023

8. The reaction of the given complex with one mole of Br2 at room temperature gave
compound A and a gas release. Compound A was found to obey the 18-electron rule.
Structural analysis of compound A indicated the presence of Rh-Br and Rh-N bonds.
Choose the correct statement(s) regarding the reaction and product A from the
following.
(i) The formal oxidation state of rhodium in compound A is +1.
(ii) The formal oxidation state of rhodium in compound A is
+3.
(iii) Two molecules of ethylene are released during the
reaction.
(iv) Compound A has two Rh-N bonds.
(v) Compound A has one Rh-N bond and two Rh-Br bonds.

9. Considering that all the Ru atoms in the given two compounds obey the 18-electron
rule, the sum of electrons donated by the three oxygen atoms according to the
neutral atom counting is,

(i) 6 (ii) 10 (iii) 12 (iv) 14

10. The reaction of (Br)Re(CO)5 with the ligand given on the right at refluxing toluene for
four hours affords product A with the evolution of a colorless gas. Heating
compound A at 270 °C for six hours gave compound B and the evolution of a colorless
gas. Compound B’s reaction with pyridine and AgOTf in refluxing toluene gave an
ionic rhenium compound C without a gas’s evolution (OTf = CF3SO3−; triflate).
Considering that compounds A, B, and C are stable, choose all the correct
statements.
(i) Compound B has three Re-N, one Re-Br, and three Re-CO bonds.
(ii) Compound A has three Re-N, one Re-Br, and four Re-CO bonds.
(iii) Compound B has three Re-N, one Re-Br, and two Re-CO bonds.
(iv) Compound C has four Re-N, one Re-Br, and two Re-CO bonds.
(v) Compound A has two Re-N, one Re-Br, and three Re-CO bonds.
(vi) Compound C has four Re-N and two Re-CO bonds.
(vii) Both compounds B and C should have one Re-Br bond.

11. Among the cobalt sandwich complexes, A-D, identify the one that can act as a one-
electron reducing agent.

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IC_Tutorial 1 II_Semester_2022-2023

12. Compound [(5-Cp)(CO)mMo(=PR)Re(CO)n] (A) has a single bond between Mo and Re

(m+n = 6; R = alkyl/aryl group). Compound A reacts with ethyl diazoacetate
(N2CHCO2Et), resulting in compound B along with the release of N2 and CO gases.
During compound B’s formation, one “:C(H)CO2Et” moiety has been inserted into the
Mo=P bond through the C atom forming a three-membered MoPC ring. Also,
compound B contains a five-membered metallacycle having both Mo and Re. Taking
the 18-electron rule as the guide, draw the structure of compounds A and B.

13. When heated in benzene, the Ni(I) complex A gave a mixture of mononuclear B and
dinuclear C Ni(0) complexes and eliminated ethane. The reaction of compound A with
dihydrogen in benzene also gave the same products (B and C) but with methane being
the side product. If compounds B and C are stable, have no bond between metal
atoms, and the metal:carbene ratio remains the same as compound A, draw their
structures.

14. The correct statements concerning the 18-electron rule are

(i) Big organometallic clusters do not obey this rule; such clusters have different
counting rules.
(ii) Organometallic compounds of early transition metals violate this rule.
(iii) Sterically bulky ligands favor the formation of complexes with 18 electrons.
(iv) Though the lanthanide metal complexes usually obey the 18-electron rule,
actinide metal complexes do not.
(v) Late transition metal complexes having square planar geometries obey this rule.

INDIAN INSTITUTE OF TECHNOLOGY DELHI, NEW DELHI-110016