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inorganic chemistry

Questions and Answers of Inorganic Chemistry

Discuss the variation in stable oxidation states for the group 11 metals, using examples of metal halides, oxides and complexes to illustrate your answer.
‘The group 12 metals differ significantly from the d-block metals in groups 4–11’. Discuss this statement.
Two complexes that have entered clinical trials as anti-cancer drugs are [HIm][RuCl4(im)(DMSO)] and [HInd][RuCl4(Ind)2]. In the search for related active complexes, [RuCl2(DMSO)2(Biim)] and
Studies of the heavier d-block metals are often used to introduce students to (a) Metal–metal bonding, (b) High coordination numbers, (c) Metal halido clusters (d)
(a) The reaction of ReCl4 and PCl5 at 570K under vacuum gives [PCl4]2[Re2Cl10]. However, when ReCl5 reacts with an excess of PCl5 at 520 K, the products are [PCl4]3[ReCl6]2 and Cl2. Comment on the
(a) ‘The salt [NH4]3[ZrF7] contains discrete ions with 7-coordinate Zr(IV). On the other hand, in a compound formulated as [NH4]3[HfF7], Hf(IV) is octahedral’. Comment on this statement and
Comment on the following statements in terms of the properties of the elements mentioned.(a) For many decades, tungsten was used to make filaments in incandescent light bulbs. Tungsten is used in
Suggest products for the following reactions (which are not necessarily balanced on the left-hand sides): (a) CsF+ XeF4 (b) SiO₂ + XeOF4 (c) XeF₂ + SbF5 (d) XeF6 + [OH] (e) KrF₂ + H₂O-
Equation 18.27 showed the preparation of [F3AsAuXe][Sb2F11] from [F3AsAu][SbF6]. Solid [F3AsAu][SbF6] contains a distorted [SbF6]− ion; one Sb–F bond is 193 pm, and five are in the range
Suggest products for the following reactions, which are not necessarily balanced on the left-hand side: (a) KrF₂ + Au (b) XeO3 + RbOH → 298 K (c) [XeC1] [Sb₂F1] (d) KrF₂ + B (OTeF5)3 (e)
(a) What is the fundamental difference between electrochromic, thermochromic and photochromic materials? (b) WO3 is widely used in electrochromic materials. Explain why WO3 is suited to this
Construct MO diagrams for He2 and [He2]+ and rationalize why the former is not known but the latter may be detected.
Confirm that the observed gas-phase structures of XeF2, XeF4 and XeF6 are consistent with the VSEPR model.
Rationalize the structure of [XeF8]2− (a square antiprism) in terms of the VSEPR model.
Why is XeCl2 likely to be much less stable than XeF2?
How would you attempt to determine values for(a) ΔfH°(XeF2, 298 K) (b) The Xe—F bond energy in XeF2?
Predict the structures of [XeO6]4−, XeOF2, XeOF4, XeO2F2, XeO2F4 and XeO3F2.
Comment on the reduction potential data in Table 19.1.Data from Table 19.1. Reduction half-equation Ca²+ (aq) + 2e Ca(s) Ti²+ (aq) + 2e Ti(s) V²+ (aq) +2e= V(s) Cr²+ (aq) +2e=Cr(s) Mn²+ (aq) +
Write a brief account of the chemistry of the xenon fluorides.
(a) The reaction of XeF2 with RuF5 at 390K results in the formation of a compound, the Raman spectrum of which is similar to that of CsRuF6 but with an additional band at 600 cm–1. Rationalize
The reaction of F2C=CClBF2 with XeF2 gives a product A for which the NMR spectroscopic data are as follows: 19F NMR δ/ppm –64.3 (s + d, J 8 Hz, 1F), –75.9 (s + d, J 138 Hz, 1F), −148.1
Structures 19.22–19.24 show bond angle data (determined by X-ray diffraction) for some complexes with low coordination numbers. Comment on these data, suggesting reasons for deviations from regular
(a) The 19F NMR spectrum of [Kr2F3][SbF6] in BrF5 at 207K contains a doublet (J = 347 Hz) and triplet (J = 347 Hz) assigned to the cation. Explain the origin of these signals.(b) Give examples that
By referring to the following literature source, assess the safety precautions required when handling XeO4: M. Gerken and G.J. Schrobilgen (2002) Inorg. Chem., vol. 41, p. 198.
For each of the following complexes, give the oxidation state of the metal and its dn configuration: (a) [Mn(CN)6]; (b) [FeC¹4]¯¯; (c) [CoCl3 (py)3]; (d) [ReO4]; (e) [Ni(en)3]2+; (f) [Ti
The vibrational modes of KrF2 are at 590, 449 and 233 cm−1. Explain why only the bands at 590 and 233 cm−1 are observed in the IR spectrum of gaseous KrF2.
Use MO theory to rationalize why the Xe—F bond strength in [XeF]+ is greater than in XeF2.
High-field NMR spectrometers, including those used for magnetic resonance imaging in hospitals, contain magnets with superconducting coils, e.g. NbTi which becomes superconducting at 9.5 K. (a)
Discharge lamps are used throughout the world for lighting and advertising. Such a lamp consists of a sealed tube with a metal electrode at each end, and contains a gas (e.g. He, Ar, Ne) or vapour
Comment on (a) The observation of variable oxidation states among elements of the s- and p-blocks, and(b) The statement that ‘variable oxidation states are a characteristic feature of any
(a) Write down, in order, the metals that make up the first row of the d-block and give the ground state valence electronic configuration of each element.(b) Which triads of metals make up groups 4,
Suggest a structure for the complex [CuCl(19.25)]+ assuming that all donor atoms are coordinated to the Cu(II) centre. N N N (19.25) N
By referring to relevant sections earlier in the book, write a brief account of the formation of hydrides, borides, carbides and nitrides of the d-block metals.
What isomers would you expect to exist for the platinum(II) compounds: (a) [Pt (H₂NCH₂CHMENH₂)2] Cl₂, and (b) [Pt (H₂NCH₂CMе₂NH₂) (H₂NCH₂ CPh₂NH₂)] Cl₂?
Give a brief overview of properties that characterize a d-block metal.
Structure 19.26 shows the ligand tpy (2,2':6',2''-terpyridine). What conformational changes does the ligand undergo when it coordinates to a metal ion? Comment on possible isomer formation in the
Suggest why (a) High coordination numbers are not usual for first row d-block metals, (b) In early d block metal complexes the combination of a high oxidation state and high coordination
Within the Kepert model, what geometries do you associate with the following coordination numbers:(a) 2; (b) 3; (c) 4; (d) 5; (e) 6
Consider the following reaction in which [P3O10]5− (see Fig. 15.21) displaces the carbonate ion to give a mixture of linkage isomers:(a) Suggest possible coordination modes for the [P3O10]5−ion
(a) Explain why complex 19.28 is chiral.(b) In each of the following reactions, the left-hand sides are balanced. Suggest possible products and give the structures of each complex formed.(c) What
Show that the trigonal bipyramid, square-based pyramid, square antiprism and dodecahedron belong to the point groups D3h, C4v, D4d and D2d respectively.
The conjugate base of 19.27 forms the complex [CoL3] which has mer-and fac-isomers. (a) Draw the structures of these isomers, and explain why the labels mer and fac are used. (b) What other type of
(a) In the solid state, Fe(CO)5 possesses a trigonal bipyramidal structure. How many carbon environments are there?(b) Explain why only one signal is observed in the 13C NMR spectrum of solutions of
Interactions between DNA and metal complexes are the basis for the use of square planar platinum(II)-containing anti-cancer drugs. (a) Explain how the interaction of right-handed DNA with chiral
(a) The following complexes each possess one of the structures listed in Table 19.4. Use the point group to deduce each structure: [ZnCl4]2− (Td); [AgCl3]2− (D3h); [ZrF7]3− (C2v); [ReH9]2−
The reaction of [RuCl2(PPh3)(dppb)] with phen leads to the loss of PPh3 and the formation of an octahedral complex, X. The structure of dppb is as follows:The solution 31P{1H} NMR spectrum of a
What chemical tests would you use to distinguish between (a) [Co(NH3)5Br][SO4] and [Co(NH3)5(SO4)]Br, and (b) [CrCl2(OH2)4]Cl·2H2O and [CrCl(OH2)5]Cl2·H2O? (c) What is the
How many different forms of [Co(en)3]3+ are possible in principle? Indicate how they are related as enantiomers or diastereoisomers.
State the types of isomerism that may be exhibited by the following complexes, and draw structures of the isomers: (a) [Co(en)2(ox)]+, (b) [Cr(ox)2(OH2)2]−,(c) [PtCl2(PPh3)2], (d)
Using spectroscopic methods, how would you distinguish between the pairs of isomers (a) cis and trans-[PdCl2(PPh3)2], (b) cis- and trans-[PtCl2(PPh3)2] (c) fac- and mer-[RhCl3(PMe3)3]?
One isomer of [PdBr2(NH3)2] is unstable with respect to a second isomer, and the isomerization process can be followed by IR spectroscopy. The IR spectrum of the first isomer shows absorptions at 480
Verify the CFSE values in Table 20.3.Table 20.3 dn dº dlo 128 628 Electronic configuration CFSE 588 128 688 High-spin weak field 688 128 = 3 -0.44 oct -0.84 oct -1.24oct -0.64 oct 0 -0.44 oct -0.84
(a) In each of the following complexes, determine the overall charge, n, which may be positive or negative: [FeII(bpy)3]n, [CrIII(ox)3]n, [CrIIIF6]n, [NiII(en)3]n, [MnII(ox)2(OH2)2]n, [ZnII(py)4]n,
(a) Which of the following octahedral complexes are chiral: cis-[CoCl2(en)2]+, [Cr(ox)3]3−, trans-[PtCl2(en)2]2+, [Ni(phen)3]2+, [RuBr4(phen)]−, cis-[RuCl(py)(phen)2]+?(b) The solution 31P NMR
(a) Explain the forms of the d orbital splitting diagrams for trigonal bipyramidal and square pyramidal complexes of formula ML5 shown in Fig. 20.11. (b) What would you expect concerning the
Outline how you would apply crystal field theory to explain why the five d-orbitals in an octahedral complex are not degenerate. Include in your answer an explanation of the ‘barycentre’.
Describe how you could use Fig. 20.23 to determine Δoct and the Racah parameter B from the energies of absorptions observed in the spectrum of an octahedral d3 ion. What are the significant
The absorption spectrum of [Ti(OH2)6]3+ exhibits a band with λmax = 510 nm. What colour of light is absorbed and what colour will aqueous solutions of [Ti(OH2)6]3+ appear?
(a) On Fig. 20.21, convert the wavenumber scale to nm.(b) Which part of the scale corresponds to the visible range? (c) What would you predict are the colours of [Ni(OH2)6]2+ and [Ni(NH3)6]2+. (d)
(a) Using data from Appendix 6, plot a graph to show how the ionic radii of high-spin, 6-coordinate M2+ ions of the first row of the d-block vary with the dn configuration. Comment on factors that
Draw the structures of the following ligands, highlight the donor atoms and give the likely modes of bonding (e.g. monodentate):(a) en; (b) bpy;(c) [CN]−; (d) [N3]−; (e)
Arrange the following ligands in order of increasing field strength: Br−, F−, [CN]−, NH3, [OH]−, H2O.
The electronic absorption spectrum of [Co(OH2)6]2+ exhibits bands at 8100, 16000 and 19400 cm–1.(a) Assign these bands to electronic transitions.(b) The value of Δoct for [Co(OH2)6]2+ listed in
For which member of the following pairs of complexes would Δoct be the larger and why: (a) [Cr(OH2)6]2+ and [Cr(OH2)6]3+ ; (b) [CrF6]3− and [Cr(NH3)6]3+;(c) [Fe(CN)6]4− and
(a) Explain why there is no distinction between low and high-spin arrangements for an octahedral d8 metal ion. (b) Discuss the factors that contribute to the preference for forming either a
Use data from Appendix 11 to predict qualitatively the outcome of the following experiment at 298 K:Cr is dissolved in excess of molar HClO4 and the solution is shaken in air.Data from Appendix 11The
In each of the following complexes, rationalize the number of observed unpaired electrons (stated after the formula): (a) [Mn(CN)6]4−(1);(b) [Mn(CN)6]2− (3); (c) [Cr(en)3]2+ (4);(d)
(a) What do you understand by the nephelauxetic effect? (b) Place the following ligands in order of increasing nephelauxetic effect: H2O, I−, F−, en, [CN]−, NH3.
Discuss each of the following observations:(a) The [CoCl4]2− ion is a regular tetrahedron but [CuCl4]2− has a flattened tetrahedral structure.(b) The electronic absorption spectrum of
The 3p2 configuration of an Si atom gives rise to the following terms: 1S0, 3P2, 3P1, 3P0 and 1D2. Use Hund’s rules to predict the relative energies of these terms, giving an explanation for your
With reference to the 3F, 1D, 3P, 1G and 1S terms of a d2 configuration, explain how you can use term symbols to gain information about allowed electronic transitions.
What term or terms arise from a d10 configuration, and what is the ground state term? Give an example of a first row d-block metal ion with this configuration.
What are the limitations of the Russell–Saunders coupling scheme?
Which of the following ions are diamagnetic:Rationalize your answer. (a) [Co(OH₂)6]³+, (b) [CoF³, (c) [NiF², (d) [Fe(CN)6]³, (e) [Fe(CN)6], (f) [Mn(OH₂)6]²+?
Deduce possible J values for a 3F term. What is the degeneracy of each of these J levels, and what happens when a magnetic field is applied? Sketch an energy level diagram to illustrate your answer,
In an octahedral field, how will the following terms split, if at all: (a) 2D, (b) 3P (c) 3F
(a) Set up a table of microstates to show that the ground term for the d1 ion is the singlet 2D. What are the components of this term in a tetrahedral field? (b) Repeat the process for a d2 ion
Discuss each of the following observations:(a) Although Co2+ (aq) forms the tetrahedral complex [CoCl4]2− on treatment with concentrated HCl, Ni2+ (aq) does not form a similar complex.(b) E° for
(a) How many ‘d–d’ bands would you expect to find in the electronic absorption spectrum of an octahedral Cr(III) complex? (b) Account for the observation that the colour of
(a) Explain clearly why, under the influence of an octahedral crystal field, the energy of the dz2 orbital is raised whereas that of the dxz orbital is lowered. State how the energies of the other
Comment on the following statements concerning electronic absorption spectra.(a) [OsCl6]3– and [RuCl6]3– exhibit LMCT bands at 282 and 348 nm, respectively.(b) [Fe(bpy)3]2+ is expected to exhibit
Rationalize why the absorption spectrum of an aqueous solution of [Ti(OH2)6]2+ (stable under acidic conditions) exhibits two well-separated bands (430 and 650 nm) assigned to ‘d–d’ transitions,
Ligand 20.12 forms an octahedral complex, [Fe(20.12)3]2+. (a) Draw diagrams to show what isomers are possible. (b) [Fe(20.12)3]Cl2 exhibits spin crossover at 120 K. Explain clearly what this
(a) The values of εmax for the most intense absorptions in the electronic spectra of [CoCl4]2− and [Co(OH2)6]2+ differ by a factor of about 100. Comment on this observation and state which complex
(a) A Kotani plot for the t2g1 configuration consists of a curve similar to that in Fig. 20.29, but levelling off at μeff ≈ 1:8 μB when kT/λ ≈ 1:0. Suggest two metal ions that you might expect
Values of the Racah parameter B for free gaseous Cr3+, Mn2+ and Ni2+ ions are 918, 960 and 1041 cm–1, respectively. For the corresponding hexaaqua ions, values of B are 725, 835 and 940 cm–1.
The structure of phthalocyanine is shown below:The complex [Cu(Pc)] is an important commercial pigment and its electronic absorption spectrum is shown in Fig. 20.40. The absorption spectrum
Find x in the formulae of the following complexes by determining the oxidation state of the metal from the experimental values of μeff : (a) [VClx(bpy)], 1.77μB; (b) Kx[V(ox)3], 2.80
Explain why in high-spin octahedral complexes, orbital contributions to the magnetic moment are only important for d1, d2, d6 and d7 configurations.
The observed magnetic moment for K3[TiF6] is 1.70 μB. (a) Calculate μ(spin-only) for this complex.(b) Why is there a difference between calculated and observed values?
Comment on the observations that octahedral Ni(II) complexes have magnetic moments in the range 2.9–3.4 μB, tetrahedral Ni(II) complexes have moments up to ≈ 4:1 μB, and square planar Ni(II)
For which of the following ions would you expect the spin-only formula to give reasonable estimates of the magnetic moment: (a) [Cr(NH3)6]3+, (b) [V(OH2)6]3+, (c)
Values of Δoct for [Ni(OH2)6]2+ and high-spin [Mn(OH2)6]3+ have been evaluated spectroscopically as 8500 and 21000 cm−1 respectively. Assuming that these values also hold for the corresponding
Comment on the modes of bonding of the ligands in the Mn(II) complexes listed at the end of Section 21.8, drawing attention to any conformational restrictions.Data from Section 21.8
(a) Which of the following complexes would you expect to suffer from a Jahn–Teller distortion: [CrI6]4−, [Cr(CN)6]4−, [CoF6]3− and [Mn(ox)3]3−? Give reasons for your answers.(b)
Suggest the formula and structure of the mononuclear complex formed between Cr3+ and ligand 21.83. Comment on possible isomerism. CO₂ N CO₂ N (21.83) CO₂
How would you attempt to (a) Estimate the crystal field stabilization energy of FeF2,(b) Determine the overall stability constant of [Co(NH3)6]3+ in aqueous solution given that the overall formation
Figure 21.44 shows the change in concentration of [MnO4]− with time during a reaction with acidified oxalate ions. (a) Suggest a method of monitoring the reaction. (b) Explain the shape of the
(a) Explain the origins of MLCT and LMCT absorptions in the electronic spectra of d-block metal complexes. Give examples to illustrate your answer.(b) Explain what information can be obtained from a
Write out, in sequence, the first row d-block elements and give the valence electronic configuration of each metal and of its M2+ ion.

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