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inorganic chemistry
Questions and Answers of
Inorganic Chemistry
Write down formulae for the following ions:(a) Manganate(VII); (b) Manganate(VI);(c) Dichromate(VI); (d) Vanadyl; (e) Vanadate (ortho and meta); (f)
Discuss the bonding between the central p-block elements in the following compounds and give the expected arrangements of the organic substituents with respect to the central E2-unit: (a)
Whether the bonding in lithium alkyls is predominantly ionic or covalent is still a matter for debate. Assuming a covalent model, use a hybrid orbital approach to suggest a bonding scheme for
Describe the gas-phase and solid state structures of Me2Be and discuss the bonding in each case. Compare the bonding with that in BeH2 and BeCl2.
The compound (Me3Si)2C(MgBr)2·nTHF is monomeric. Suggest a value for n and propose a structure for this Grignard reagent.
(a) Discuss the variation in structure for the group 13 trialkyls and triaryls. (b) Comment on features of interest in the solid state structures of [Me2(PhC2)Ga]2 and [Ph3Al]2.
The following equilibrium has been studied by 119Sn NMR and Mossbauer spectroscopies:The 119Sn Mossbauer spectrum of a solid sample of RSnSnRPh2 at 78K provided evidence for the presence of three
The conversion of (kC1-C5Me5)2SiBr2 to (η5-C5Me5)2Si is achieved using anthracene/potassium. Outline the role of this reagent.
The structures of R2E = ER2 molecules where E is C, Si, Ge or Sn are usually of type A or B shown below:The bonding in the E2-units is described in terms of the interaction of two triplet R2E centres
(a) Suggest how Na will react with MeC(CH2SbCl2)3.(b) Comment on aspects of the bonding in the following compound:(c) Cp2Ba and (C5Me5)2Ba both have polymeric structures in the solid state. However,
Suggest the nature of the solid state structures of(a) Ph2PbCl2, (b) Ph3PbCl,(c) (2,4,6-Me3C6H2)3PbCl (d) [PhPbCl5]2−. In each case, state the expected coordination environment of the Pb
Suggest products when Et3SnCl reacts with the following reagents: (a) H2O; (b) Na[Cp]; (c) Na2S;(d) PhLi; (e) Na.
(a) In what ways do the solid state structures of (η5-C5R5)2Sn for R = H, Me and Ph differ? (b) In the solid state structure of (η5-C5Me5)2Mg, the two cyclopentadienyl rings are
Suggest products when Me3Sb reacts with the following reagents: (a) B2H6; (b) H2O2; (c) Br2;(d) Cl2 followed by treatment with MeLi; (e) MeI; (f) Br2 followed by treatment
Write a brief account of how the changes in available oxidation states for elements, E, in groups 13 to 15 maffect the families of organoelement compounds of type RnE that can be formed.
Give methods of synthesis for the following families of compound, commenting where appropriate on limitations in the choice of R: (a) R4Ge; (b) R3B;(c) (C5R5)3Ga; (d)
Give a short account of the structural variation observed for cyclopentadienyl derivatives CpnE of the heavier p-block elements.
Write a brief account of the use of sterically demanding substituents in the stabilization of compounds containing E–E and E = E bonds where E is a p-block metal or semi-metal.
Write a short account describing methods of formation of metal–carbon bonds for metals in the s- and p-block.
Comment on the following:(a) Infrared spectra of [V(CO)6]− and Cr(CO)6 show absorptions at 1859 and 1981 cm−1 respectively assigned to νCO, and 460 and 441 cm−1 assigned to νMC.(b) The Tolman
(a) Draw a structure corresponding to the formula(b) The 1H NMR spectrum of the complex in part (a) contains a quintet centred at δ–10.2 ppm. Assign the signal and explain the origin of the
(a) Explain the meaning of the following notations:(b) Why can the cyclopentadienyl and CO ligands be regarded as being versatile in their bonding modes?(c) Is PPh3 a ‘versatile ligand’? μ-CO;
Give examples of the synthetic utility of the [B(C6F5)4]− and [CHB11Me5Br6]− anions, and rationalize the choice of these anions in the examples that you describe.
Rationalize the following observations.(a) On formingthe C–C bond in C2(CN)4 lengthens from 135 to 151 pm.(b) During the photolysis of Mo(CO)5(THF) with PPh3, a signal in the 31P NMR spectrum at δ
(a) In 1956, it was concluded on the basis of dipole moment measurements that Cp2Pb did not contain coparallel C5-rings. Explain how this conclusion follows from such measurements.(b) X-ray
Treatment of (2,4,6-tBu3C6H2)P=P(2,4,6-tBu3C6H2) with CF3SO3Me gives a salt A as the only product. The 31P NMR spectrum of the precursor contains a singlet (δ+495 ppm), while that of the product
The solution 1H NMR spectrum of the tetrahedral clusterexhibits the following signals at room temperature: δ/ppm 0.53 (s, 36H), 1.41 (m, 8H), 2.25 (s, 24H), 2.36 (s, 24H), 3.59 (m, 8H), 4.29
The structure of was determined by single crystal X-ray diffraction in 1975, and by neutron diffraction in 2004. In both structure determinations, the bridging H atoms were located. To what extent
Draw a bonding scheme (similar to that in Fig. 24.7b) for the interaction of an η3-allyl ligand with a low oxidation state metal centre.Figure 24.7b.
Derive a CBC classification for: (a) W(CO)6 5 (b) (n³-Cp)2 WH2 (c) WMe6 (d) (15-Cp)₂Fe (e) (nᵒ-C6H6)₂Cr (f) (nº-C6H6)Cr(CO)3
(a) The reaction between BiCl3 and 3 equivalents of EtMgCl yields compound X as the organo product. Two equivalents of BiI3 react with 1 equivalent of X to produce 3 equivalents of compound Y. In the
Showthat the metal centres in the following complexes obey the 18-electron rule: (a) (n³-Cp)Rh(n²-C₂H4) (PMe3) (b) (n³-C3H5)2 Rh (μ-Cl)₂ Rh(n³-C3H5) 2 (c) Cr(CO)4 (PPH3)2 (d) Fe(CO)3
Comment on the following observations:(a) In the IR spectrum of free MeCH=CH2, ν̅C=C comes at 1652 cm−1, but in the complexthe corresponding absorption is at 1504 cm−1.(b) At 303 K, the 1H NMR
Experimentally determined analytical data for PhSeCl3 are C, 27.5; H, 1.8; Cl, 39.9%. An X-ray diffraction study of PhSeCl3 shows that it forms polymeric chains in the solid state, with each Se
The International Marine Organization is, implementing a ban on the use of tributyltin compounds in anti-fouling paints on ships. The [Bu3Sn]+ cation is leached from paints into the water where it
Comment on:(a) The use of trimethylorganometallics in the manufacture of III–V semiconductors;(b) The application of R3Al compounds as catalysts.
The CBC model shows that within the chemistry of Mn, ≈ 79% of compounds fall into the MnL5X class. Show that each of the following fits this description and that each has a value of EN = 18. (a)
What is a synergic effect, and how does it relate to metal–carbonyl bonding?
In Section 24.8, we stated that the distribution of the products in Fig. 24.18 is consistent with the migration of the Me group, and not with a mechanism that involves movement of the ‘inserted’
With reference to Box 23.2, develop a qualitative bonding scheme for (η5-Cp)2Fe.Box 23.2. THEORY Box 23.2 Bonding in cyclopentadienyl complexes: ³-mode If all five C atoms of the cyclopentadienyl
(a) Os5(CO)18 has a metal framework consisting of three edge-sharing triangles (a raft structure). Show that the valence electron count for this raft is consistent with the number available.(b)
Within covalent bond classification (CBC), what is the difference between L, X and Z ligands? Use a simple MO approach to illustrate your answer.
In the Heck reaction (eq. 24.87), the active catalyst is Pd(PPh3)2. Write equations to show (a) oxidative addition of PhBr to Pd(PPh3)2 to give A, (b) Addition of CH2=CHCO2Me to A followed by
The reaction of 1,3-dimethylimidazolium iodide (shown on the next page) with one equivalent of KOtBu in THF, followed by addition of one equivalent of Ru3(CO)12 leads to product A. The IR spectrum of
Explain why scheme 24.98 is invoked to explain the equivalence of the H atoms in each terminal CH2 group of an η3-allyl ligand, rather than a process involving rotation about the metal–ligand
Reaction of Fe(CO)5 with Na2[Fe(CO)4] in THF gives a salt Na2[A] and CO. The Raman spectrum of [Et4N]2[A] shows an absorption at 160 cm−1 assigned to an unbridged Fe–Fe bond. Suggest an identity
Suggest possible structures for the cation in [Fe2(NO)6][PF6]2 and state how you would attempt to distinguish between them experimentally.
Use Wade’s rules (PSEPT) to suggest structures for Os7(CO)21 and [Os8(CO)22]2−.
(a) Suggest structures for the complexes LFe(CO)3 where L = 2,5-norbornadiene (24.23) or cycloheptatriene.(b) How is the bonding mode of the cycloheptatriene ligand affected on going from LFe(CO)3
For each of the following clusters, confirm that the total valence electron count is consistent with the metal cage framework adopted: (a) [Ru6(CO)18]2−, octahedron; (b) H4Ru4(CO)12,
(a) Confirm that H2Os3(CO)11 has sufficient valence electrons to adopt a triangular metal framework. Do the modes of bonding of the CO and H ligands affect the total valence electron count? Comment
Suggest products in the following reactions, and give likely structures for the products: (a) Fe(CO)5 irradiated with C2H4; (b) Re2(CO)10 with Na/Hg;(c) Na[Mn(CO)5] with ONCl; (d)
Suggest possible products for the following reactions: (a) (c) (d) OcFe Oc OCTi. oc ос ос I H Me Me CO [PhzC][BF4] PhC=CPh AgBF4 in McCN hu
Illustrate, with examples, what is meant by (a) Oxidative addition, (b) Reductive elimination, (c) α-hydrogen abstraction, (d) β-hydrogen elimination,(e) Alkyl
The reaction of Cr(CO)6 with Ph2P(CH2)4PPh2 leads to the formation of two products, A and B. The 31P NMR spectrum of A shows two signals (δ + 46.0 and –16.9 ppm, relative integrals 1 : 1), while
Ferroquine has passed clinical phase II trials as an antimalarial drug. Both enantiomers of ferroquine are equally active in vitro. Explain why the molecule is chiral, and draw the structure of
Discuss the following statements:(a) Complexes Fe(CO)3L where L is a 1,3-diene have applications in organic synthesis.(b) The fullerenes C60 and C70 form a range of organometallic complexes.(c)
Around 10 Mt per year of acetic acid are manufactured worldwide and ≈25% of this is produced using the CativaTM process. The reaction:is catalysed by cis-[IrI2(CO)2]−. Methanol is first converted
Explain the difference between a Fischer-type carbene and a Schrock-type carbene.
Suggest products in the following reactions: (a) Excess FeCl3 with (η5-Cp)2Fe; (b) (η5-Cp)2Fe with PhC(O)Cl in the presence of AlCl3; (c) (η5-Cp)2Fe with toluene in the presence of
Ruthenium(II) complexes of the general type shown below are potential anticancer drugs:The cytotoxicity of such complexes relies upon the replacement of the chlorido ligand by H2O, and is pH
(a) Analyse the catalytic cycle shown in Fig. 25.19, identifying the types of reactions occurring. (b) Why does this process work best for R' = vinyl, benzyl or aryl groups?Figure 25.19.
In the reaction of ferrocene with MeC(O)Cl and AlCl3, how could one distinguish between the products Fe(η5-C5H4C(O)Me)2 and (η5-Cp)Fe(η5-C5H4C(O)Me) by methods other than elemental analysis and
The compound drawn below is an example of a ferrocenophane:It undergoes ring-opening polymerization (ROP) to yield a high molecular weight polymer in which the Cp rings in each ferrocene are parallel
The reaction of [(C6Me6)RuCl2]2 (A) with C6Me6 in the presence of AgBF4 gives [(C6Me6)2Ru][BF4]2 containing cation B. Treatment of this compound with Na in liquid NH3 yields a neutral Ru(0) complex,
Describe the bonding in (η4-C4H4)Fe(CO)3, accounting for the diamagnetism of the complex.
The isomerization of alkenes is catalysed by HCo(CO)3 and Fig. 25.20 shows the relevant catalytic cycle. (a) HCo(CO)4 is a catalyst precursor; explain what this means. (b) Give a fuller description
Suggest a suitable catalyst for the following reaction, and outline the initial steps in the mechanism of the reaction: n CO₂Me CO₂Me MeO₂C CO₂Me
Comment on each of the following statements.(a) Re2(CO)10 adopts a staggered conformation in the solid state, whereas [Re2Cl8]2− adopts an eclipsed conformation.(b) In anions of type [M(CO)4]n−,
(a) The cluster H3Os6(CO)16B contains an interstitial B atom and has an Os6 cage derived from a pentagonal bipyramid with one equatorial vertex missing. Comment on this structure in terms of both
Reduction of Ir4(CO)12 with Na in THF yields the salt Na[Ir(CO)x] (A) which has a strong absorption in its IR spectrum (THF solution) at 1892 cm−1. Reduction of A with Na in liquid NH3, followed by
Give equations that illustrate each of the following processes. Define any abbreviations used.(a) Cross-metathesis between two alkenes.(b) Alkyne metathesis catalysed by a high oxidation state metal
Outline the catalytic processes involved in the manufacture of acetic acid (Monsanto process) and acetic anhydride (Tennessee–Eastman process), and compare the catalytic pathways.
(a) Of the following alkenes, which are prochiral: PhHC = CHPh, PhMeC = CHPh, H2C = CHPh, H2C = C(CO2H)(NHC(O)Me)?(b) If an asymmetric hydrogenation proceeds with 85% ee favouring the R-enantiomer,
(a) Assuming some similarity between the mechanism of hydroformylation using HCo(CO)4 and HRh(CO)(PPh3)3 as catalysts, propose a mechanism for the conversion of RCH=CH2 to RCH2CH2CHO and explain what
A crucial component of a dye-sensitized solar cell (DSC) is the sensitizer. The latter captures photons which are converted to electric current in the cell. A typical dye is cis-[Ru(L)2(NCS–N)2]
Comment on the following observations:(a) The density of HfO2 (9.68 g cm−3) is much greater than that of ZrO2 (5.73 g cm−3).(b) NbF4 is paramagnetic but NbCl4 and NbBr4 are essentially
Suggest products in the following reactions: (a) CsBr heated with NbBr5 at 383 K; (b) KF and TaF5 melted together; (c) NbF5 with bpy at 298 K. (d) Comment on the structures of the
TaS2 crystallizes with a layer structure related to that of CdI2, whereas FeS2 adopts a distorted NaCl structure. Why would you not expect TaS2 and FeS2 to crystallize with similar structure types?
Comment on the observation that K3[Cr2Cl9] is strongly paramagnetic but K3[W2Cl9] is diamagnetic.
(a) The complex shown below is the first example of a Pd(IV) complex containing a nitrosyl ligand (see also structure 20.9 for another view of the tridentate ligand). On the basis of the assignment
(a) Interpret the formula [Mo6Cl8]Cl2Cl4/2 in structural terms, and show that the formula is consistent with the stoichiometry MoCl2. (b) Show that the [W6Br8]4+ cluster can be considered to
The ligand shown at the end of the problem, 16-S-4, forms the complex [Hg(16-S-4)]2+. The solution 1H NMR spectrum of [Hg(16-S-4)][ClO4]2 consists of two signals at δ 3.40 and 2.46 ppm with relative
Give a short account of Tc(V) and Re(V) oxido species.
Comment on each of the following observations:(a) Unlikehas an electronic absorption spectrum that is the sum of those of the constituent ions.(b) AgI is readily soluble in saturated aqueous AgNO3,
Briefly summarize similarities and differences between Mn and Tc chemistries.
Draw the structure of [Re2Cl8]2−. Discuss the metal–metal bonding in the anion and its consequences on ligand orientation.
Suggest reasons for the variation in Re—Re bond lengths in the following species: ReCl4 (273 pm), Re3Cl9, (249pm), [Re2Cl9]2− (224 pm), [Re2Cl9]− (270 pm) and [Re2Cl4 (μ-Ph2PCH2CH2PPh2)2] (224
(a) Figure 22.37 shows eight corner-sharing ReO6 octahedra in the solid state structure of ReO3. From this, derive a diagram to show the unit cell of ReO3. Explain the relationship between your
When K2[OsCl4] is heated with NH3 under pressure, compound A of composition Os2Cl5H24N9 is isolated. Treatment of a solution of A with HI precipitates a compound in which three of the five chlorines
Give an account of the halides of Ru and Os.
(a) Give an account of the methods of synthesis of Rh(IV) and Ir(IV) halides and halido anions.(b) Reaction of [IrCl6]2− with PPh3 and Na[BH4] in EtOH gives [IrH3(PPh3)3]. Give the structures of
(a) Rationalize why each of the following is diamagnetic: [Os(CN)6]4−, [PtCl4]2−, OsO4 and trans-[OsO2F4]2−.(b) Solution 77Se and 13C NMR spectra for the octahedral anions in the compounds
[Ir(CN)6]3− has a regular octahedral structure. For K3[Ir(CN)6], the wavenumbers corresponding to the C≡N stretching modes are 2167 (A1g), 2143 (Eg) and 2130 (T1u) cm–1. (a) To which point
Myochrysine contains the thiomalate ligand and is an anti-arthritic drug and has a polymeric structure in the solid state:The backbone of the polymer is a helical chain of alternating Au and S atoms,
When RhBr3 in the presence of MePh2As is treated with H3PO2, a monomeric compound X is formed. X contains 2Br and 3MePh2As per Rh, and is a non-electrolyte. Its IR spectrum has a band at 2073 cm−1,
(a) Compare the structures of β-PdCl2 and [Nb6Cl12]2+. (b) Discuss, with examples, the existence (or not) of Pt(III) species. (c) Discuss the variation in stereochemistries of Ni(II),
(a) Describe the methods by which cis- and trans-[PtCl2(NH3)2] can be distinguished from each other and from [Pt(NH3)4][PtCl4]. (b) Another possible isomer would be
Suggest products in the reactions of K2[PtCl4] with(a) Excess KI; (b) Aqueous NH3; (c) phen; (d) tpy;(e) Excess KCN. What are the expected structures of these products?
Complexes of the type [PtCl2(R2P(CH2)nPR2)] may be monomeric or dimeric. Suggest factors that might influence this preference and suggest structures for the complexes.
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