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1 Preferably without using reference material, write out the 3d elements in their arrangement in the periodic table.

lndicate the metal ions that commonly form tetrahedral complexes of formula [MX4]2- where X is a halide ion. 2 (a) On a chart of the d-block elements in their periodic table arrangement, identify the elements and associated oxidation numbers that form square-planar complexes. (b) Give formulas for three examples of square-planar complexes. 3 (a) Sketch the two structures that describe most six-coordinate complexes. (b) Which one of these is rare? (c) Give formulas for three different d-metal complexes that have the more common six-coordinate structure. 4 Name and draw structures of the fallowing complexes: (a) [Ni(CO)4]; (b) [Ni(CN)4)2- (c) [CoCI4]2- (d) [Ni(NH3)6]2+. 5 Draw the structures of representative complexes that contain the ligands (a) en, (b) ox2-, (c) phen, and (d) edta46 Draw the structure of (a) a typical square-planar four-coordinate complex; (b) a typical trigonal prismatic six-coordinate complex; (c) a typical complex of coordination number 2. Name each complex. 7 Give formulas for (a) pentaamminechlorocobalt(lll) chloride, (b) hexaaquairon(3+) nitrate; (c) cis-dichlorobis(ethylenediamine)ruthenium(ll); (d) mhydroxobis[pentaamminechromium(lll)] chloride. 8 Name the octahedral complex ions (a) cis-[CrCl2(NH3)4]+, (b) trans-[Cr(NCS)4(NH3)2]-, and (c) [Co(C204)(en)2)+. Is the oxalato complex cis or trans? 9 Draw all possible isomers of (a) octahedral [RuCI2(NH3)4], (b) square-planar [lrH(CO)(PR3)2], (c) tetrahedral [CoCI3(0H2)]-, (d) octahedral [lrCl3(PEt3)3], and (c) octahedral [CoCl2(en)(NH3)2]+. 10 The compound Na2lrCl5 reacts with triphenylphosphine in diethylene glycol under an atmosphere of CO to give trans-[lrCl(CO)(PPh3)2], known as Vaska's compound. Excess CO produces a five-coordinate species and treatment with NaBH4 in ethanol gives [lrH(CO)2(PPh3)2]. Draw and name the three complexes. 11 Which of the following complexes are chiral? (a) [Cr(ox)3]3-, (b) cis-[PtCI2(en)], (c} cis(RhCI2(NH3)4]+ , (d) [Ru(bipy)3]2+, (e) [Co(edta)]-, (f) fac-[Co(N02)3(dien)], (g) mer[Co(N02)3(dien)I. Draw the enantiomers of the complexes identified as chiral and identify the plane of symmetry in the structures of the achiral complexes. 12 One pink solid has the formula CoCl3 5NH3 H2O. A solution of this salt is also pink and rapidly gives 3 mol AgCI on titration with silver nitrate solution. When the pink solid is heated, it loses 1 mol H20 to give a purple solid with the same ratio at NH3:CI:Co. The purple solid releases two of its chlorides rapidly; then, on dissolution and after titration with AgNO3, releases one of its chlorides slowly. Deduce the structures of the two octahedral complexes and draw and name them.

13 The hydrated chromium chloride that is available commercially has the overall composition CrCl3 6H2O. On boiling a solution, it becomes violet and has a molar electrical conductivity similar to that of [Co(NH3)6]Cl3. In contrast, CrCI3.5H20 is green and has a lower molar conductivity in solution. If a dilute acidified solution of the green complex is allowed to stand for several hours, it turns violet Interpret these observations with structural diagrams. 14 The complex first denoted as b-[PtCI2(NH3)2] was identified as the trans isomer (the cisisomer was denoted a) It reacts slowly with solid Ag2O to produce [Pt(NH3)2(OH2)2]2+. This complex does not react with ethylenediamine to give a chelated complex. Name and draw the structure of the diaqua complex. 15 The third isomer' (neither a nor b, see Exercise 14) of composition PtCI2.2 NH3, is an insoluble solid which, when ground with AgNO3, gives a solution containing [Pt(NH3)4](N03)2 and a new solid phase of composition Ag2[PtCI4]. Give the structures and names of each of the three Pt(ll) compounds. 16 Phosphine and arsine analogs of [PtCl2(NH3)2j were prepared in 1934 by Jensen. He reported zero dipole moments for the beta isomers, where the beta designation represents the product of a synthetic route analogous to that of the ammines. Give the structures of the complexes. 17 In trans-[W(CO)4(PR3)2, the alkylphosphine ligands define the z- axis of the coordinate system. Sketch the symmetry-adapted linear combination of s orbitals from the two P atoms that can combine with the metal dz2 orbital. Show the bonding and antibonding orbitals that may be formed. 18 Determine the configuration (in the form t2gm egn or em t2n as appropriate), the number of unpaired electrons, and the Iigand-field stabilization energy as a multiple of DO or DT for each of the following complexes using the spectrochemical series to decide, where relevant, which are likely to be strong-field and which weak-field (a) (Co(NH3)6]3+,.(b) [Fe(OH2)6]2+, (c) [Fe(CN)6]3-, (d) (Cr(NH3)6]3+, (e) [W(CO)6 (f) tetrahedral [FeCl4]2-, and (g) tetrahedral [Ni(CO)4]. 19 Both H- and P(Ph)3 are Iigands of similar fie[d strength high in the spectrochemical series. Recalling that phosphines act as p acceptors, is p-acceptor character required for strong-field behaviour? What orbital factors account for the strength of each ligand? 20 Estimate the spin-only contribution to the magnetic moment for each complex in Exercise 18. 21 Solutions of the complexes.[Co(NH3)6]2+, (Co(H20)2+ (both Oh) and [CoCl4]2- - are coloured. One is pink, another is yellow, and the third is blue. Considering the spectrochemical series and the relative magnitudes DT and DO try to assign each colour to one of the complexes 22 (a) The most complexes in biosystems contain chelating ligands. Describe properties of chelating ligands and give reasons for the latter statement. (b) Chelating properties are not favorable in any case. When and why is labile bonding important?

23 (a) What is the interconnection between function and content of metal ions in the human body? (b) Si- and Al-compounds are not preferentially used in biosystems. Why? (c) Define the term essential element. (d) Give examples for non essential elements in the human body. 24 (a) Numerate the general functions of metal ions in biosystems. (b) Give examples for the application of metal ion complexes in medicine. (c) Describe the term therapeutic width. (d) Sketch the Lewis formula of cis-Pt, explain the main biological feature of cis-Pt for its use as anti-carcinogen? 25 Define the following terms: (a) Apoenzyme, (b) Charge transfer complex, (c) Coenzyme 26 (a) What are the functions of a catalyst? (b) Numerate the general features of the molecular structure of enzymes. (c) The stabilization of an enzyme-substrate complex is unfavorable for catalytic activity. Why? 27 (a) What is the function of proteins in BiC? (b) Describe the model for the anti-oxidantfunction of Se-containing proteins

28 (a) Sketch the Lewis formula of a porphyrine core. (b) Why are porphyrines stable, why are the colored? (c) Give examples for the use of porphyrine complexes in biosystems, including the derivates of the prophyrine. (d) Describe the d-orbital level of porphyrine complexes. 29 (a) Describe the mechanism of uptake and release of Fe in biosystems (oxidation states, pH dependence). (b) Sketch the functional groups used as Siderophores. (c) Numerate the molecular properties of Apo- and Holo-Transferritin. 30 (a) Describe the main mechanisms of the electrolyte transport in the human body. (b) What are Ionophores, do you know analogs from the lab? (c) Why can ionophores be used as antibiotics? (d) Sketch the flip-flop mechanism of the Na-K-pump. 31 (a) Numerate the most important functions of Mg in biosystems. (b) Describe the reaction mechanism for the hydrolysis of ATP by Lewis formulas. (c) Why are pseudorotations important for the function of MgATPase?