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inorganic chemistry

Questions and Answers of Inorganic Chemistry

Given the following mechanism for the formation of a chelate complex,derive the rate law for the formation of the chelate. Discuss the step that is different from that for two monodentate ligands.
Discuss the following set of rate constants (k) and activation parameters for water exchange reactions of metal aqua ions.
Use the concept particularly the effects of penetration and shielding on the radial wavefunction, to account for the variation of single-bond covalent radii with position in the periodic table.
Suggest chemical reagents that would be suitable for carrying out the following transformations and write balanced equations for the reactions:(a) Oxidation of HCl to chlorine gas, (b) Reduction
Construct thermodynamic cycles for the reactions of Cr or Mo with dilute acids and thus consider the importance of metallic bonding in determining the standard reduction potentials for formation of
Write balanced equations for the reactions that each of the following species might undergo in aerated aqueous acid. If the species is stable, write ‘no reaction’. (a) Cr2+, (b)
Write balanced equations for the reactions, including disproportionations, that can be expected for each of the following species in aerated acidic aqueous solution: (a) Fe2+, (b)
Sketch the qualitative splitting pattern and relative intensities within each set for the 1H- and 31P-NMR spectra of PH3.
Use the references in Z.W. Pan, Z.R. Dai, and Z.L. Wang (Science, 2001, 291, 1947) as a starting point to write a review of wire-like nanomaterials of Group 13 elements. Indicate how In2O3 nanobelts
Sketch the general form of the Frost diagrams for phosphorus (oxidation states 0 to +5) and bismuth (0 to +5) in acidic solution and discuss the relative stabilities of the +3 and +5 oxidation states
Predict which oxoanions of sulfur will disproportionate in acidic conditions.
Predict whether SeO32− is more stable in acidic or basic solution.
Construct Frost diagrams for the Group 6 elements Cr, Mo, and W in acidic conditions. Use these diagrams to predict (a) Which oxidation state of each element is most oxidizing (b) Whether
Construct a Frost diagram for mercury in acidic solution. Comment on the tendency for [Hg2]2+ to disproportionate.
Explain why [FeF6]3− is almost colourless whereas [CoF6]3− is coloured and exhibits only a single band in the visible region of the spectrum.
If a substitution process is associative, why may it be difficult to characterize an aqua ion as labile or inert?
Consider the complexes (18) and (19) discussed in the Brief illustration in Section 21.11. Think about the potential routes of the electron transfer in the two complexes and suggest why there is such
The reactions of [Ni(CO)4] in which phosphines or phosphites replace CO to give [Ni(CO)3L] all occur at the same rate regardless of which phosphine or phosphite is being used. Is the reaction d or a?
The complex [PtH(PEt3)3]+ was studied in deuterated acetone in the presence of excess PEt3. In the absence of excess ligand the 1H-NMR spectrum in the hydride region exhibits a doublet of triplets.
Write the rate law for formation of [MnX(OH2)5]+ from the aqua ion and X−. How would you determine if the reaction is d or a?
Refer to Table 21.13 and calculate the rate constants for electron transfer in the oxidation of by the oxidants (a) (b) Comment on the relative sizes of the rate constants.Table 21.13. [V(OH₂)
Solutions of [PtH2(PMe3)2] exist as a mixture of cis and trans isomers. Addition of excess PMe3 led to formation of [PtH2(PMe3)3] at a concentration that could be detected using NMR. This complex
Figure 21.24 (which is based on J.B. Goddard and F. Basolo, Inorg. Chem., 1968, 7, 936) shows the observed first-order rate constants for the reaction of [PdBrL]+ with various Y− to give [PdYL]+,
Octahedral complexes of metal centres with high oxidation numbers or of d metals of the second and third series are less labile than those of low oxidation number and d metals of the first series of
Calculate the rate constants for outer-sphere reactions from the following data. Compare your results to the measured values in the last column. Reaction Cr²+ + Fe³+ [W(CN),]++ Ce(IV) [Fe(CN),]+
The activation enthalpy for the reduction of cis-[CoCl2(en)2]+ by Cr2+ (aq) is −24 kJ mol−1. Explain the negative value.
The rate of loss of chlorobenzene, PhCl, from [W(CO)4L(PhCl)] increases with increase in the cone angle of L. What does this observation suggest about the mechanism?
The pressure dependence of the replacement of chlorobenzene (PhCl) by piperidine in the complex [W(CO)4(PPh3)(PhCl)] has been studied. The volume of activation is found to be +11.3 cm3 mol−1. What
In the presence of catalytic amounts of [Pt(μ-P2O5H2)4]4−(21) and light, 2-propanol produces H2 and acetone (E.L. Harley, A.E. Stiegman, A. Vlcek, Jr, and H.B. Gray, J. Am. Chem. Soc., 1987, 109,
From the spectrum of [CrCl(NH3)5]2+ shown in Fig. 20.33, propose a wavelength for photoinitiation of reduction of Cr(III) to Cr(II) accompanied by oxidation of a ligand.Figure 20.33. 200 λ
Does the fact that [Ni(CN)5]3− can be isolated help to explain why substitution reactions of [Ni(CN)4]2− are very rapid?
Suppose that you are given a series of metal tricarbonyl compounds having the respective symmetries C2v, D3h, and Cs. Without consulting reference material, which of these should display the greatest
Design two-step syntheses of cis-and trans-[PtCl2(NO2)(NH3)]− starting from [PtCl4]2−.
How does each of the following modifications affect the rate of a square-planar complex substitution reaction? (a) Changing a trans ligand from H− to Cl−; (b) Changing the leaving group
Discuss the following data for M−M and M−CO bond enthalpies in a series of metal carbonyl cluster compounds. The enthalpies given in each case are average values for that compound. Fe(CO), Fe,
The rate of attack on [Co(OH2)6]3+ by an entering group Y is nearly independent of Y, with the spectacular exception of the rapid reaction with OH−. Explain the anomaly. What is the implication of
Predict the products of the following reactions:(a) [Pt(PR3)4]2+ + 2Cl−(b) [PtCl4]2− + 2PR3(c) cis-[Pt(NH3)2(py)2]2+ + 2Cl−
Put in order of increasing rate of substitution by H2O the complexes (a) [Co(NH3)6]3+, (b) [Rh(NH3)6]3+, (c) [Ir(NH3)6]3+,(d) [Mn(OH2)6]2+, (e) [Ni(OH2)6]2+.
State the effect on the rate of dissociatively activated reactions of Rh(III) complexes of (a) An increase in the overall charge on the complex, (b) Changing the leaving group from NO3−
Write out the inner-and outer-sphere pathways for reduction of azidopentaamminecobalt (III) ion with V2+(aq). What experimental data might be used to distinguish between the two pathways?
The compound [Fe(SCN)(OH2)5]2+ can be detected in the reaction of [Co(NCS)(NH3)5]2+ with Fe2+(aq) to give Fe3+(aq) and Co2+(aq). What does this observation suggest about the mechanism?
The rate of reduction of [Co(NH3)5(OH2)]3+ by Cr(II) is seven orders of magnitude slower than reduction of its conjugate base, [Co(NH3)5(OH)]2+, by Cr(II). For the corresponding reductions with
The photochemical substitution of [W(CO)5(py)] (py = pyridine) with triphenylphosphine gives [W(CO)5(P(C6H5)3)]. In the presence of excess phosphine, the quantum yield is approximately 0.4. A flash
Name the species, draw the structures of, and give valence electron counts to the metal atoms in: (a) [Fe(CO)5],(b) [Mn2(CO)10], (c) [V(CO)6], (d) [Fe(CO)4]2−, (e)
Propose the structure of the product obtained by the reaction of [Re(CO)(η5-C5H5)(NO)(PPh3)]+ with Li[HBEt3]. The latter contains a strongly nucleophilic hydride.
(a) Sketch an η2 interaction of 1,3-butadiene with a metal atom.(b) Do the same for an η4 interaction.
When several CO ligands are present in a metal carbonyl, an indication of the individual bond strengths can be obtained by means of force constants derived from the experimental IR frequencies. In
What hapticities are possible for the interaction of each of the following ligands with a single d-block metal atom such as cobalt? (a) C2H4, (b) Cyclopentadienyl, (c) C6H6,(d)
Draw plausible structures and give the electron count of(a) [Ni(η3-C3H5)2], (b) η4-cyclobutadiene-η5-cyclopentadienylcobalt,(c) [Co(η3-C3H5)(CO)2]. If the electron count deviates from
It is often possible to assign different resonance structures to an organometallic compound; for example, there can be competition between carbene and zwitterionic forms. Suggest ways of
State the two common methods for the preparation of simple metal carbonyls and illustrate your answer with chemical equations. Is the selection of method based on thermodynamic or kinetic
Agostic interactions are often thought of as weak. Discuss examples where agostic interactions have been shown to displace other ligand interactions. See B.L. Conley and T.J. Williams, J. Am. Chem.
Describe how alkane complexes of d metals have been unambiguously identified by NMR. What additional insights can be gained from X-ray diffraction? See S. Geftakis and G.E. Ball, J. Am. Chem. Soc.,
Provide plausible reasons for the differences in IR stretching frequencies between each of the following pairs: (a) [Mo(CO)3(PF3)3] 2040, 1991 cm−1 versus [Mo(CO)3(PMe3)3] 1945, 1851
It is possible to distinguish two types of notionally agostic interactions: agostic and anagostic. Describe the differences between the two types. See M. Brookhart, M.L.H. Green, and G. Parkin, Proc.
The compound [Ni3(C5H5)3(CO)2] has a single CO stretching absorption at 1761 cm−1. The IR data indicate that all C5H5 ligands are pentahapto and probably in identical environments. (a) On the
The dinitrogen complex [Zr2(η5-Cp*)4(N2)3] has been isolated and its structure determined by single-crystal X-ray diffraction. Each Zr atom is bonded to two Cp* and one terminal N2. The third N2
Decide which of the two complexes (a) [W(CO)6](b) [Ir(CO)Cl(PPh3)2] should undergo the fastest exchange with 13CO. Justify your answer.
How might you unambiguously identify, in solution, an organometallic complex containing a noble gas atom as a ligand?
β-Pinene is a major component of natural turpentine and its polymer is nontoxic and used in a wide variety of industrial applications such as adhesives, varnishes, food packaging and chewing gum.
The tethering of a homogeneous catalyst to a solid support has been investigated as a method that allows easy separation of the catalyst from the reaction mixture, with little loss in catalyst
Suggest syntheses of (a) [Mo(η7-C7H7)(CO)3]BF4 from [Mo(CO)6] (b) [Ir(COMe)(CO)(Cl)2(PPh3)2] from [Ir(CO) Cl(PPh3)2].
A. Arbaoui and C. Redshaw (Polym. Chem., 2010, 1, 801) review catalysts for the synthesis of biodegradable polymers via ring opening metathesis polymerization. Summarize the need for biodegradable
Na[W(η5-C5H5)(CO)3] reacts with 3-chloroprop-1-ene to give a solid, A, which has the molecular formula [W(C3H5) (C5H5)(CO)3]. Compound A loses carbon monoxide on exposure to light and forms compound
It is possible to consider bridging carbonyl ligands in several different ways, with differing numbers of electrons donated to metals. Describe how it is possible to account for the structure of
Give the probable structure of the product obtained when [Mo(CO)6] is allowed to react first with LiPh and then with the strong carbocation reagent, CH3OSO2CF3.
Rearrangements of ligands so that differing numbers of carbons interact with the central metal atom are known as haptotropic rearrangements. Consider the (fluorenyl)(cyclopentadienyl) iron complex.
Propose two syntheses for [MnMe(CO)5], both starting with [Mn2(CO)10], with one using Na and one using Br2. You may use other reagents of your choice.
Compare and contrast Fischer and Schrock carbenes.
Using the 18-electron rule as a guide, indicate the probable number of carbonyl ligands in (a) [W(η6-C6H6)(CO)n],(b) [Rh(η5-C5H5)(CO)n],(c) [Ru3(CO)n].
What conclusions can you draw from the bonding and reactivity of dihydrogen bound to a low-oxidation-state d-block metal that might be applicable to the bonding of an alkane to a metal? What
Which metal carbonyl in each of (a) [Fe(CO)4]2− or [Co(CO)4]−, (b) [Mn(CO)5]− or [Re(CO)5]− should be the most basic towards a proton? Explain your answer.
When direct evidence for a mechanism is not available, chemists frequently invoke analogies with similar systems. Describe how J.E. Bäckvall, B. Åkermark, and S.O. Ljunggren (J. Am. Chem. Soc.,
When [Fe(CO)5] is refluxed with cyclopentadiene, compound A is formed which has the empirical formula C8H6O3Fe and a complicated 1H-NMR spectrum. Compound A readily loses CO to give compound B with
Treatment of TiCl4 at low temperature with EtMgBr gives an organometallic compound that is unstable above −70°C. However, treatment of TiCl4 at low temperature with MeLi or LiCH2SiMe3 gives
Treatment of TiCl4 with 4 equivalents of NaCp gives a single organometallic compound (together with NaCl byproduct). At room temperature the 1H-NMR spectrum shows a single sharp singlet; on cooling
How may the use of two liquid phases that are not miscible at room temperature be used to create catalytic systems that have advantages over normal (single phase) systems? Discuss this area, paying
Give the equations for workable reactions that will convert [Fe(η5-C5H5)2] into (a) [Fe(η5-C5H5)(η5-C5H4COCH3)](b) [Fe(η5-C5H5)(η5-C5H4CO2H)].
(a) Starting with the alkene complex shown in Fig. 22.22 with trans-DHC=CHD in place of C2H4, assume dissolved OH− attacks from the side opposite the metal. Give a stereochemical drawing of the
Infrared spectroscopic investigation of a mixture of CO, H2, and 1-butene under conditions that bring about hydroformylation indicate the presence of compound (E) in Fig. 22.20 in the reaction
The rates of H2 gas absorption (in dm3 mol−1 s−1) by alkenes catalysed by [RhCl(PPh3)3] in benzene at 25ºC are: hexene, 2910; cis-4-methyl-2-pentene, 990; cyclohexene, 3160; 1-methylcyclohexene,
Write a plausible mechanism, giving your reasoning, for the reactions (a) [Mn(CO),(CF₂)]++ H₂O → [Mn(CO),]++ 2HF (b) [Rh(CO)(C₂H₂) (PR3)₂] → [RhH(CO) (PR₂)₂] + C₂H₂
Based on isolobal analogies, choose the groups that might replace the group in bold in (a) [Co₂(CO),CH]: OCH3, N(CH3)2, or SICH, (b) [(OC),MnMn(CO),]: I, CH₂, or CCH
(a) Give a balanced equation for the reaction of any of the lanthanoids with aqueous acid. (b) Justify your answer with reduction potentials and with a generalization on the most stable positive
Draw the catalytic cycle for the Ziegler Natta polymerization of propene. Explain each of the steps involved and predict what the physical properties of the polymer produced would be like.
Sketch the catalytic cycle for the production of butanal from prop-1-ene. Identify the step at which selectivity to the n or iso isomer occurs.
Addition of PPh3 to a solution of Wilkinson’s catalyst, [RhCl(PPh3)3], reduces the turnover frequency for the hydrogenation of propene. Give a plausible mechanistic explanation for this observation.
Ligand substitution reactions on metal clusters are often found to occur by associative mechanisms, and it is postulated that these occur by initial breaking of an M–M bond, thereby providing an
(a) What cluster valence electron (CVE) count is characteristic of octahedral and trigonal prismatic complexes?(b) Can these CVE values be derived from the 18-electron rule?(c) Determine the probable
Suggest two plausible routes by which a carbonyl ligand in [Mo(Cp)(CO)3Me] might exchange for a phosphine. Neither route should invoke the initial dissociation of a CO.
The compound [Ni(η5-C5H5)2] readily adds one molecule of HF to yield [Ni(η5-C5H5)(η4-C5H6)]+, whereas [Fe(η5-C5H5)2] reacts with strong acid to yield [Fe(η5-C5H5)2H]+. In the latter compound the
Sketch the a1′ symmetry-adapted orbitals for two eclipsed C5H5 ligands stacked together with D5h symmetry. Identify the s, p, and d orbitals of a metal atom lying between the rings that may have
Lanthanoid coordination compounds rarely exhibit isomerism in solution. Suggest two factors that might cause this phenomenon, explaining your reasoning. (See D. Parker, R.S. Dickins, H. Puschmann, C.
Explain the variation in ionic radii between La3+ and Lu3+.
Neither lanthanoid nor actinoid organometallic compounds obey the 18-electron rule. Discuss the reasons, using the structures of the tris(Cp) and tris(Cp*) Ln and An complexes as examples.
From a knowledge of their chemical properties, speculate on why cerium and europium were the easiest lanthanoids to isolate before the development of ion-exchange chromatography.
The catalytic activity of many organolanthanoids is controlled by the ionic radius of Ln3+. In general Ln(Cp*)2X complexes that are catalysts for olefin polymerization show decreasing reactivity as
Explain why Nd(C5H5)3 rapidly exchanges its cyclopentadienyl ligands with Cl− and many other anions, but the cyclopentadienyl ligands in U(C5H5)3 are not labile.
‘Quantum cutting’ is a process by which absorption of a single high-energy photon, corresponding to incident light in the UV spectral region, results in the emission of two photons of lower
‘Single molecule magnets’ (abbreviated SMMs) offer intriguing new possibilities for storing and processing data: lanthanoids, due to their large number of unpaired electrons, are attracting a

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