Inorganic Chemistry

Part 1A Sample paper

_____________________________________________________________________ Candidates should answer 5 questions in three hours Numbers in square brackets indicate the approximate weight to be given to each part of the question _____________________________________________________________________

Question 1

Answer three of the following parts (equal marks to each part):

(i) Determine the point groups of two of the following compounds and indicate the symmetry elements involved on a sketch of the structure: [Cr(bipy)3]3+, PF5, B2H6, S4N4, [(CO)4Mo(bipy)] (ii) Which of the following complexes obey the eighteen electron rule? [Fe(CN)6]3- , [V(CO)6], [IrCl(CO)(PPh3)2], [(5-C5H5)Ni(NO)], WMe6 (iii) What isomers are possible for complexes of three of the following empirical formulations and how might they be distinguished ? CrCl3(NH3)4, PtCl2(NH3)2, Cr(H2O)6Cl3, Co(NH3)5(NO2)Cl2 (iv) Derive the term symbol for the ground state in the gas phase of three of the following ions: Ti2+, Fe3+, Eu2+, Pr3+, Cl-

(v) Determine the number of ir active element-halogen stretching vibrations for one of the following: ClF3 BF3 XeF5+ [AuCl4]SiF4

Question 2

Answer all parts. Provide explanations for ALL of the following data or statements, indicating where appropriate where they illustrate general features of the chemistry of the transition metals: (i) CrCl2 has a very different solid state structure from MoCl2 (ii) Paramagnetic complexes are far less common for Re than for Mn. [3] [3]

(iii) The sublimation energy for Re metal is 704 kJmol-1 whereas that for Mn metal is 220.5 kJmol-1. [3] (iv) [NiCl4]2- is paramagnetic in solution at all temperatures whereas the complex [NiCl2(PPh2Bun)2] is paramagnetic at room temperature but diamagnetic at higher temperatures. [3] (v) The standard redox potentials (in volts) for Mn, Tc and Re redox couples at 25oC and pH 0 are: MnO4-/MnO2 TcO4-/TcO2 ReO4-/ReO2 1.69 +0.74 +0.51 [4]

(vi) The Cr(III) complex [Cr(NH3)6]Cl3 has a regular octahedral structure and is stable whereas the Cr(II) counterpart [Cr(NH3)6]Cl2 has a distorted structure and loses coordinated ammonia very readily. [4]

Question 3 Answer BOTH parts (i) Suggest syntheses (which may involve more than one step) for TWO of the following compounds using the precursor materials indicated. [Rh( -C5H5)(CO)(PMe3)] from [Rh2(2-Cl)2(CO)4]. [Ti( -C5H5)2Me2] from TiCl4. [Mo( -C7H7)(CO)3]+ from [Mo(CO)6]. [Mn( -C3H5)(CO)4] from Na[Mn(CO)5]. [Fe( -C5H4COMe)( -C5H5)] from FeCl2.
5 5 3 7 5 5

[5]

(ii) Identify the products A to G in the following reaction sequences. Make full use of the data given and show your reasoning clearly. Indicate the structures of the products you suggest. Refluxing n-decane solutions of [Fe2(2-CO)3(CO)6] and cyclopentadiene (C5H6) give a binuclear compound A which has the empirical formula C14H10Fe2O4. Compound A has two very different (CO) bands in its infrared spectrum at 1960 and 1765 cm-1. Reduction of A with two equivalents of sodium amalgam in tetrahydrofuran solution gives B which has two (CO) absorptions in its infrared spectrum at 2015 and 1910 cm-1, and which reacts with MeI to give C and a white, water soluble side-product D. The dicarbonyl compound C shows two singlets in its 1H NMR spectrum in the ratio 5:3. Chloroform solutions of compound A react with aqueous hydrochloric acid / hydrogen peroxide mixtures to give the red compound E which has the empirical formula C7H5ClFeO2. The compound E shows only a simple singlet in its 1H NMR spectrum and has two (CO) bands in its infrared spectrum at 2055 and 1950 cm-1. Compound E reacts with MeLi to give C and a white compound F which is highly soluble in water. Compound C reacts with trimethyl phosphine (PMe3) to give the new compound G and no side-products. Compound G is formed as a racemic mixture and shows one (CO) metal carbonyl absorption in its infrared spectrum, along with another strong band at 1680 cm-1 which is absent in PMe3 and C. The 1H NMR spectrum of G shows three signals in the ratio 5:3:9.

Question 4

Answer ALL parts (a) Discuss briefly the use of X-ray powder diffraction in analytical inorganic chemistry [4] (b) Distinguish between the terms lattice and structure as used in crystallography. [4] (c) Under what circumstances can a subset of reflections be systematically absent from the diffraction pattern of a crystalline solid. Mathematical derivations are not required. [3] (d) The X-ray powder diffraction pattern, recorded using CuK1 radiation (= 1.5406 ), of a cubic binary iron oxide contains intensity maxima at the following scattering angles ( i.e. 2 in degrees): 18.27 30.05 35.39 37.02 43.01 47.09 53.36 56.88

Index the lines, identify the lattice type and determine the unit cell lattice parameter of the material. Give reasons for your assignment of lattice type. [9] NB 1 = 100 pm

Question 5 Answer all parts:

(i) Given that for a first row transition element M the irreducible representations spanned by the metal orbitals are 4s a1g, 4p t1u, 3d eg and t2g and that the SALCS for 6 sigma donor ligands L span a1g, t1u and eg, construct a MO diagram for the sigma bonding in the complex ML6 . Label all orbitals appropriately. [6] (ii) Explain the effect on the energies of the MOs of the complex of : (a) Increasing the M-L interaction. (b) Increasing the charge on the metal ion. [4]

(iii) By means of a simplified MO scheme indicate the qualitative effect of including -donation and -acceptor orbitals on the ligands. [4]

(iv) Hence predict the number of unpaired electrons in [FeF6]3-, [Fe(CN)6]3- and [Ru(H2O)6]2+. [3]

(v) Comment briefly on any similarities or differences between your MO scheme and the bonding picture derived from Crystal Field Theory. [3]

Question 6

1. Answer ALL of the following parts, providing explanations where possible: (i) Give an expression in terms of concentrations for the STEPWISE stability constants K1 and K2 for the reaction of [M(H2O)6]2+ with ligand L.

[3]

(ii) Calculate the Crystal Field Stabilisation Energy (CFSE) in terms of the crystal field splitting parameter for [M(H2O)6]2+ with M = Fe2+, Co2+ and Zn2+ (note H2O is a weak field ligand). Hence arrange in sequence the K1 values for reaction of the hexaquo ions with L. [4] (iii) What is the chelate effect and what is its origin ? [2]

(iv) Why are octahedral Cu2+ complexes often distorted from regular octahedral geometry ? What is the driving force for this distortion and how does it affect the value of K1? [3] (v) What is the effect on K1 if the ligand L is an anion ? (vi) Referring where appropriate to the above, account for the trends in stability constants shown in the figure below. [2] [6]

Question 7 Answer ALL parts (i) Comment on the data below and indicate the extent to which it illustrates a general feature of the chemistry of main group elements. [6]

Sum of first three ionisation energies

8000

Sum of IE's kJ/mol

7000

6000

5000

4000 B Al Ga In Tl

(ii) Discuss the structures and bonding of the products obtained from the reactions of NH3 with halides of phosphorus. [4] (iii) Identify compounds A to E in the scheme below, drawing their structures and commenting on the data provided. [10]

D+E O2 NO [Me4N]O2 C

A condense at 77oK

[Fe(CO)5] B
Question continues

A is a diamagnetic solid B has an RMM of 172 C is a salt containing a reactive ion that rearranges to form nitrate in aqueous solution D is a brown paramagnetic gas E is a colourless diamagnetic gas in equilibrium with D

[2] [2]

[2] [2] [2]

Question 8 Answer all parts (i) For the reaction 3MX2(s) 2MX3(s) + M(s) (M = lanthanide) Construct a thermodynamic cycle in terms of lattice enthalpies L, ionisation energies I1, I2 and I3 heats of atomisation Hatm, and the heat of formation Hm of MX3(s) from MX2(s) . [4] (ii) How do the lattice enthalpies change across the lanthanide series ? [2]

(iii) Given that I1 and I2 change linearly across the lanthanide series, use the diagram below to discuss the stabilities of the divalent states of the lanthanides. [6]

Trends in term (2I3 Hatm) for lanthanide elements

5000

4500

4000

3500

3000

2500 La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

(iv) Comments on points of interest of two of the following compounds: [U(C8H8)2], UF6, [(C5Me5)2LuMe], [UO2(acac)2]

(acac = CH3COCHCOCH3)

10