Chemistry of Coordination Compounds Introduction to Metal Complexes 24.4 242 243 (a) (e) (a) (b) ‘A metal complex consists of a central metal ion bonded to a number of surrounding molecules or ions. The number of bonds formed by the central metal ion is the coordination number. The surrounding molecules or ions are the ligands. A Lewis acid is an electron pair acceptor and a Lewis base is an electron pair donor. All ligands have at least one unshared pair of valence electrons. Metal ions have empty valence orbitals (d, s or p) that can accommodate donated electron pairs. Ligands act as electron pair donors, or Lewis bases, and metal ions act as electron air acceptors, or Lewis acids, via their empty valence orbitals. In Werner's theory, primary valence is the charge of the metal cation at the center of the complex. Secondary valence is the number of atoms bound or coordinated to the. central metal ion. The modern terms for these concepts are oxidation state and coordination number, respectively. (Note that ‘oxidation state’ is a broader term than ionic charge, but Wemer’s complexes contain metal ions where cation charge and ‘oxidation state are equal.) Ligands are the Lewis base in metal-ligand interactions (see Solution 24.1(b)). AS ‘such, they must possess at least one unshared electron pair. NH, has an unshared electron pair but BH,, with less than 8 electrons about B, has no unshared electron pair and cannot act as a ligand. In fact, BH, acts as a Lewis acid, an electron pair acceptor, because itis electron-deficient. Analyze/Pian. Follow the logic in Sample Exercises 24.1 and 24.2. Solve: ) (b) () This compound is electrically neutral, and the NH, ligands carry no charge, so the charge on Ni must balance the -2 charge of the 2 Br-ions. The charge and oxidation state of Niis +2. Since there are 6 NH, molecules in the complex, the likely coordination number is 6. In some cases Br~ acts as a ligand, 50 the coordination number could be other than 6. ‘Assuming that the 6 NH, molecules are the ligands, 2 Br~ ions are not coordinated to the Ni*, so 2 mol AgBr(s) will precipitate. (If one or both of the Br~ act as a ligand, the mol AgBr(s) would be different.) 60824 Coordination Compounds Solutions to Exercises 244 24.5 246 247 248 (2) Yes. There are 6 possible ligands, 3 H,O molecules and 3 Ct-ions. Any Cr ions that are not coordinated to the metal will form AgCi(s) precipitate when the complex is treated with AgNO,(aq). Absence of AgCi(s) would mean all Cr ions were ligands and. a coordination number of 6. One mole of AgCl(s) per mole of complex would mean one uncoordinated ligand, and so on. This assumes that all 3 H,O molecules act as ligands. In fact, they could serve as water of hydration (Section 13.1, A Closer Look: Hydrates). Reaction with AgNO, gives no information about the nature of H,O molecules. (b) Yes. ‘Conductivity is directly related to the number of ions in a solution. The lower the conductivity, the more CI ions that act as ligands. Conductivity measurements on a set of standard solutions with various moles of ions per mole of complex would provide a comparative method for quantitative determination of the number of free and bound Cr ions. (a) Coordination number = 4, oxidation number = +2 (b) 5.44 (0) 6,43 (4) 5,42 (€) 643 (f) 4,42 {@) Coordination number = 6, oxidation number = +3 (b) 6,42 (c) 6,44 (4) 6,42 (€) 6,43 (f) 6,43 octahedral Analyze/Pian. Given the formula of a coordination compound, determine the number and kinds. of donor atoms. The ligands are enclosed in the square brackets. Decide which atom in the ligand has an unshared electron pair itis likely to donate. Solve: () 4cr_— (be) 4Cr, 10% (e) 4N,20r (@) SC. InN”, both C and N have an unshared electron pair. Cis less electronegative and more likely to donate its unshared pair. (e) 60. C,0,-is a bidentate ligand: each ion is bound through 2 © atoms for a total of 6 0 donor atoms. () _4N. enis.a bidentate ligand bound through 2 N atoms. (2) 6 C (see Solution 24.7() (bd) 50,1Br- (ce) 3N,3Br- (d) 20,4N ) 20,28 () 4N,2F Polydendate ligands; Nomenclature 24.9 (2) Amonodendate ligand binds toa metal in through one atom, a bidendate ligand binds through two atoms. (>) _ Ifa bidentate ligand occupies two coordination sites, three bidentate ligands fill the coordination sphere of a six-coordinate complex24 24.10 24.11 24.12 24.13 24.14 Coordination Compounds Solutions to Exercises (©) __Atridentate ligand has at least three atoms with unshared electron pairs in the correct orientation to simultanously bind one or more metal ions. (2) 2 coordination sites, 2N donor atoms (©) 2 coordination sites, 2 N donor atoms (©) 2 coordination sites, 2 © donor atoms (Although there are four potential © donor ‘atoms in C,0,%, itis geometrically impossible for more than two of these to be bound toa single metal ion. (4) 4 coordination sites, 4 N donor atoms, 6 coordination sites, 2 N and 4 O donor atoms: Analyze/Plan. Given the formula of a coordination compound, determine the number of coordination sites occupied by the polydentate ligand. The coordination number of the complexes is either 4 or 6. Note the number of monodentate ligands and determine the number of coordination sites occupied by the polydentate ligands. Solve: (@) ortho-phenanthroline, o-phen, is bidentate (0) oxalate, C,0,7, is bidentate (©) ethylenediaminetetraacetate, EDTA, is pentadentate (0) ethylenediamine, en, is bidentate @4 4 (6 WE (2) The term chelate effect means there is a special stability associated with formation ‘of a metal complex containing a polydentate (chelate) ligand relative to a complex containing only monodentate ligands. (b) When a single chelating ligand replaces two or more monodendate ligands, the number of free molecules in the system increases and the entropy of the system increases. Chemical reactions with +AS tend to be spontaneous, have negative AG, and large positive values of K,, (©) Polydentate ligands can be used to bind metal ions and prevent them from undergoing unwanted chemical reactions without removing them from solution. The polydentate ligand thus hides or sequesters the metal ion. (2) Monodentate: py has only one N donor atom. (>) —_K,, for this reaction will be less than one. Two free pyridine molecules are replaced by one free bipy molecule. There are more moles of particles in the reactants than products, so AS is predicted to be negative. Processes with a net decrease in entropy are usually nonspontaneous, have positive AG, and values of K,, less than one. This equilibrium is likely to be spontaneous in the reverse direction, 61024 24.15 24.16 24.17 Coordination Compounds Solutions to Exercises Analyze/Plan. Given the name of a coordination compound, write the chemical formula. Refer to Table 24.2 to find ligand formulas. Place the metal complex (metal ion + ligands) square brackets and the counter ion (if there is one) outside the brackets. Soive: (a) [Cr(NH,)J(NO,), (b)_ [Co(NH,),CO,],S0, (c) [Pt(en),C!,]Br, (@) KIVH,0),8r,) (e) [2n(en),IIHg!,) (a) [Mn(H,0),BrSO, (6) [Ru(bipy)](NO,), (€) [Fe(o-phen),Cl,]CIO, (d)_Na[Co(en)Br,) (©) [Ni(NH,)els[Cr(0x)3}, Analyze/Plan. Follow the logic in Sample Exercise 24.4, paying attention to naming rules in Section 24.3. Solve: (2) _tetraamminedichlororhodium(ill) chloride {b) potassium hexachiorotitanate(IV) (©) _tetrachlorooxomolybdenum(VI) (4) tetraaqua(oxalato)platinum(IV) bromide 24.18 (a) __ trichloroethylenediamineniobium(V) sulfate (b) _tricarbonyitripyridinemolybdenum(0) () ‘ammonium tetrachloroaurate(|t!) (4) _tetraamminediaquairidium(ti) nitrate Isomerism 24.19 Analyze/Plan. Consider the definitions of the various types of isomerism, and which of the 24.20 complexes could exhibit isomerism of the specified type. Solve: ONO, _oNo ONO, NH @) Pee Poe (©) [PA(NHs)2(ONO)a}, [Pa(NHs)-(NOz)2} HAN’ ‘NH HSN’ ‘ONO cis trans " NIIUN NA |_UN: (co) Vy i Dv () [Co(NH3).Br2]Cl, [Co(NH3)48rCI]8: CK : ei (d) [Co(NH3)Br2]Cl, [(Co(NH),8rCi]8r NH; a NH; a HN NHS (a) Cot 0. “TN. ZT HON yy, SCN HON fy, NES coordination sphere isomerism 61124 Coordination Compounds Solutions to Exercises 24.20 24.24 24.22 24.23 (continued) cl cl ch T NH Ne I Fak) ° AVN APN Or ay NH HANTS Han HM ns Han We, NH © Dex, err oot cir Hany Ch HN I Br coordination sphere isomerism Yes. A tetrahedral complex of the form MA,B, would have neither structural nor stereoisomers. For a tetrahedral complex, no differences in connectivity are possible for a single central atom, so the terms cis and trans do not apply. No optical isomers with tetrahedral geometry are possible because M is not bound to four different groups. The ‘complex must be square planar with cis and trans geometric isomers. ‘Two geometric isomers are possible for an octahedral MA,B, complex (see below). All other arrangements, including mirror images, can be rotated into these two structures. Neither isomer is optically active. A B BL| 8 BIB Av lB ATTA A A @ i) Analyze/Plan. Follow the logic in Sample Exercises 24.5 and 24.6. Solve: NHy NHy = ae Me] 7 nv 7el CK > ¢ JPN N N >) G1 N trans cis The cis isomer is chiral. 61224 Coordination Compounds Solutions to Exercises 24.23 (continued) NH, ai mize ok; eo) 24.24 Coke “oa che ral ta, a ‘The symbol N_N represents the bidentate ligand (bipy). ‘There are no optical isomers. The mirror image of each structural isomer can be ‘superimposed on the structure above by a 180° rotation. 24.25 Analyze/Plan. Follow the logic in Sample Exercise 24.5 and 24.8. Solve: (a) ote () [on /PHs]” Cl PHs]” ofc a Zn He L ci PH; we er cis trans © Sid trans optical isomers (The three isomeric complex ions in part (c) each have a 1+ charge.) 2428 (a) (Ch © ck ,2. The dy, d.. and d,, metal orbitals point between the x, y, and z axes, ‘and electrons in these orbitals experience less repulsion with ligand electrons. Thus, in the presence of an octahedral ligand field, the d,,,d,, and d,, metal orbitals are lower in energy than the dj» and d,: 61424 24.33 24.34 24.35 24.36 24.37 24.38 Coordination Compounds Solutions to Exercises — 42 -y2 432 (@) jee >| dy. dee. dyz {b) The magnitude of A and the energy of the d-d transition for a d' complex are equal (©) The spectrochemical series is an ordering of ligands according to their ability to increase the energy gap A. 10 Jos «2.998 x () AE =hen= £526 10* Jes = 2.998 10° m/s < 3973x499 500 « 10m = 3.97 « 10°" Jiphoton 10? A =3.973 x 10° Jiphoton x 8.922% 10 photons. ah = 220.25 = 239 kslmol mol 7000 (&) _ If H,O is replaced by NH,, the magnitude of A would increase because NH, is higher in the spectrochemical series and creates a stronger ligand field. Analyze/Plan. Consider the relationship between the color of a complex, the wavelength of absorbed light and the position of a ligand in the spectrochemical series. Solve: Cyanide is a strong field ligand. The d-d electronic transitions occur at relatively high energy, because A is large. A yellow color corresponds to absorption of a photon in the violet region of the visible spectrum, between 430 and 400 nm. H,0 is a weaker field ligand than CN". The blue or green colors of aqua complexes correspond to absorptions in the region of 620 nm. Cleary, this is a region of lower energy photons than those with characteristic wavelengths in the 430 to 400 nm region. These are very general and imprecise comparisons. Other factors are involved, including whether the complex is high spin or low spin, The ions absorb the complement of the color they appear. Green [Ni(H,O),}*" absorbs red light, 650-800 nm. Purple [Ni(NH,),J”* absorbs yellow light, 560-580 nm. Thus, [Ni(NH,).* absorbs light with the shorter wavelength. This agrees with the spectrochemical series, which indicates that H,O will produce a smaller d orbital splitting (A) than NH,. Thus, [Ni(H,O).?* ‘should absorb light with a smaller energy and longer wavelength. Analyze/Plan. Determine the charge on the metal ion, subtract it from the row number (3-12) of the transition metal, and the remainder is the number of d-electrons. Solve: (a) Ru*,d® —(b) Cu, d?_—(c) Co, d* —(d) Mo™,d' (2) Re™, d* (a) Fe*,d® — (b) Mn**,d°_—(c) Co™.d’— (d) Ag’, d= (e) Sr, d° 61524 Coordination Compounds Solutions to Exercises 24.39 Analyze/Pian. Follow the logic in Sample Exercise 24.9. Solve: 24.40 24.41 24.42 (2) Mn: [Arl4s*3d* (b) Ru: [kr}Ss"4d” (©) Rh: [Kr]5s'4d* Mn: [Arjad* Ru*: [Krad Rh®: (Kr}4g ] 4 Tat 44 Uy 2 unpaired electrons ‘unpaired electron ——_O unpaired electrons (2) Ru: [KrjSs'4d’ —(b)_Mo: [krjSs'4a° (©) Co: [Arl4s*3d” Ru: [kr]4d® Mo**: [Kr]3d* Co*: [Arjad” { 1 4 HUTA ti HTT 4 unpaired electrons 4 unpaired electrons 3 unpaired electrons Analyze/Pian. All complexes in this exercise are six-coordinate octahedral. Use the definitions of high-spin and low-spin along with the orbital diagram from Sample Exercise 24.9 to place electrons for the various complexes. Solve: @ » FO © 4%, high spin 48, high spin d%, low spin © © » 4H (a) ) fT (©) a 5, high spin 8, low spin © [ATTA ) 0) alt Fh TH ae ds 61624 Coordination Compounds Solutions to Exerci: 24.43 Analyze/Plan. Follow the ideas but reverse the logic in Sample Exercise 24.9. Solve: AL 4 Al4 high spin 24.44 i Ut TTT [Fe(CN),}* [Fe(NCS)_)* low spin high spin Both complexes contain Fe™, a d® jon. CN", a strong field ligand, produces such a large A that the splitting energy is greater than the pairing energy, and the complex is low spin. NCS- produces a smaller A, so it is energetically favorable for d electrons to be unpaired in the higher energy d orbitals. NCS-is a much weaker-field ligand than CN”. Itis probably weaker than NH, and near H,0 in the spectrochemical series. Additional Exercises 24.45 (a) —_[Ni(en),CLJ:_[Ni(en),(H,0),]Cl, (b) —KINI(CN),J; [Zn(H,0),(NO,),; [Cu(NH,),]SO, (©) [CoFP*, high spin; [Co(NH,},)** or [Co(CN},)™, low spin (@) thiocyanate, SCN or NCS"; nitrite, NO," or ONO (©) _[Cofen},CL]CI; see Exercise 24.25(c) for another example. © [Cofen),}Cl,, KefFe(ox)3) 24.46 [PL(NH,)eICly; [Pt(NH,),CLJCl; [P(NH,)ChICH [PtNH,),ClJ; KIP(NH;)CI] cl ae HO 2447 (a) | HO] Ot (b) | HOLL OH, H,07] “oH, [72° H,0~ | ~OH, Ho Ho [RUHOCICh = > [RUH_O}C!, oe +3er 61724 Coordination Compounds Solutions to Exercises 24.48 (a) 2 (b) 2 NH H,0. Ba ct wl H,0~ | NH, cl er NH ci octahedral octahedral © of a) oO ¥ “tee NA — Cl Co: °) Ru: C r™ nT Scr HO CN octahedral octahdedral 24.49 (a) [24.48(a)] cis-tetraamminediaquacobalt(|!) nitrate [24.48(b)] sodium aquapentachlororuthenate(II!) [24.48(c)] ammonium trans-diaquabisoxalatocobaltate(II!) [24.48(d)] cis-dichlorobisethylenediamineruthenium(I!) (bo) Only the complex in 24.48(d) is optically active. The mirror images of (a)-(c) can be ‘superimposed on the original structure. The chelating ligands in (d) prevent its mirror images (enantiomers) from being superimposable. (24.50 (a) Valence electrons: 2P + 6C + 16H = 10 + 24+ 16 =50¢e-, 25 pr (b) Both CO and dmpe are neutral molecules, so the oxidation state of Mo must be zero. (o) (H atoms omitted for clarity) C=0 coordinates through C, because itis less electronegative than O, and a better electron pair donor. The molecule has only a single isomer. The dmpe ligand cannot span trans positions, so there are no geometric isomers. The mirror image of the structure above is easily superimposable, so there are no optical isomers. 61824 Coordination Compounds Solutions to Exercises 24.51 (a) _ Ina square planar complex such as [Pt(en)Cl,, if one pair of ligands is trans, the remaining two coordination sites are also trans to each other. Ethylenediamine is a relatively short bidentate ligand that cannot occupy trans coordination sites, so the trans isomer is. unknown. (&) A polydentate ligand such as EDTA necessarily occupies trans positions in an ‘octahedral complex. The minimum steric requirement for a bidentate ligand is a medium-length chain between the two coordinating atoms that will occupy the trans positions. In terms of reaction rate theory, itis unlikely that a flexible bidentate ligand will be in exactty the right orientation to coordinate trans. The polydentate ligand has ‘a much better chance of occupying trans positions, because it locks the metal ion in place with multiple coordination sites (and shields the metal ion from competing ligands present in the solution). 24.52 We will represent the end of the bidentate ligand containing the CF, group by a shaded oval, the other end by an open oval: 4 wf ) (1 yD ae SS OS 24.53. (a) __Hemogiobin is the iron-containing protein that transports O, in human blood. (b) Chlorophylis are magnesium-containing porphyrins in plants. They are the key components in the conversion of solar energy into chemical energy that can be used by living organisms. (©) __Siderophores are iron-binding compounds or ligands produced by a microorganism. ‘They compete on a molecular level for iron in the medium outside the organism and carry needed iron into the cells of the organism. 24.54 (a) AgCi(s) + 2NH,(aq) > [Ag(NH,),1"aq) + Cr(aq) () —[Cr(en),Ci,}CK(aq) + 2H,0() > [Cr(en,)(H,0),}"(aq) + 3Cr(aq) green brown-orange ‘3Ag"(aq) + 3Cr(aq) > 3AgCi(s) {Cr(en),(H,0),)* and 3NO,-are spectator ions in the second reaction. (©) _Zn(NO,),(aq) + 2NaOH(aq) > Zn(OH),{s) + 2NaNO,(aq) ‘Zn(OH),(s) + 2NaOH(aq) > [Zn(OH,),J*(aq) + 2Na‘(aq) (@) —- Co*(aq) + 4Cr(aq) > [CoCl, (aq) 61924 24.55 24.56 24.57 24.58 24.59 Coordination Compounds Solutions to Exercises (a) _pentacarbonyliron(0) (b) Since CO is a neutral molecule, the oxidation state of iron must be zero. (©) [Fe(CO),CN} has two geometric isomers. In a trigonal bipyramid, the axial and equatorial positions are not equivalent and not superimposable. One isomer has CN in an axial position and the other has it in an equatorial position. oof" ° oc, NS NS Fe—CO Fe—CN “} oc} co co The ligands that possess the greatest ability to interact with the central metal atom cause the largest splitting. The properties of ligands that are important are charge (usually the more negatively charged ligands produce larger splittings) and polarizability, which measures the ability of the ligand to distort its charge distribution as it interacts with the positively charged metal ion. (a) leftshoe — (c) wood screw —(e)_a typical golf club (a) La] > a (>) These complexes are colored because the crystal-field splitting energy, A, is in the Visible portion of the electromagnetic spectrum. Visible light with A = hol/A is absorbed, promoting one of the d electrons into a higher energy d orbital. The ‘remaining wavelengths of visible light are reflected or transmitted; the combination of these wavelengths is the color we see. (©) _ [VF,}* will absorb light with a longer wavelength and lower energy. As a weak-field ligand in the spectrochemical series, F- causes a smaller A than H,O. Since A and ‘Aare inversely related, smaller A corresponds to longer A. (2) _ Formally, the two Ru centers have different oxidation states; one is +2 and the other is +3. © RAE Ru | | 4 TA Tay ATT 62024 Coordination Compounds Solutions to Exercises 24.60 24.61 24.62 (©) _ Theres extensive bonding-electron delocalization in the isolated pyrazine molecule. When pyrazine acts as a bridging ligand, its delocalized molecular orbitals provide a pathway for delocalization of the “odd” d electron in the Creutz-Taube ion. The two metal ions appear equivalent because the odd d electron is delocalized across the pyrazine bridge. ‘According to the spectrochemical series, the order of increasing A for the ligands is Cr < HO appears yellow, so it is absorbing violet light of approximately 420 nm. The wavelength of the LMCT transition for chromate, 420 nm, is shorter than the wavelength of LCMT transition in permanganate, 565 nm. This means that there is a larger energy difference between filled ligand and empty metal orbitals in chromate than in permanganate. Yes. Awhite compound indicates that no visible light is absorbed. Going left on the Periodic chart from Mn to Cr, the absorbed wavelength got shorter and the energy difference between ligand and metal orbitals increased. The 420 nm absorption by Cr0,-'s at the short wavelength edge of the visible spectrum. tis not surprising that the ion containing V, further left on the chart, absorbs at a still shorter wavelength in the ultraviolet region and that VO, appears white. Application of pressure would result in shorter metal ion- oxide distances. This would have the effect of increasing the ligand-electron repulsions, and would result in a larger splitting in the d orbital energies. Thus, application of Ti Pressure should result in a shift in the absorption toa higher ‘energy and shorter wavelength. 62224 Coordination Compounds Solutions to Exerci: 24.66 (a) nc. | cn Fe’ no~ | ™~, (>) sodium dicarbonyltetracyanoferrate(|I) (©) #2, 6delectrons (6) We expect the complex to be low spin. Cyanide (and carbonyl) are high on the spectrochemical series, which means the complex will have a large A splitting characteristic of low spin complexes. 2487 3 x oS TP 0 0. Ln On gn A s<_ Soo ot a b | Sor u i ons : ° i 24.68 (a) Onlyone (0) Two ° ! Cy Cores) as KD rans (c) Four; two are geometric, the other two are stereoisomers of each of these. oF ° 1 62324 Coordination Compounds Solutions to Exercises 24.69 WT) 4, + be ye For a d® metal ion in a ‘strong ligand field, there would be two unpaired electrons. Integrative Exercises 24.70 Ina complex ion, the transition metal is an electron pair acceptor, a Lewis acid; the ligand is an electron pair donor, a Lewis base. In carbonic anhydrase, the Zn* ion withdraws electron density from the © atom of water. The electronegative oxygen atom compensates by withdrawing electron-density from the O-H bond. The O-H bond is polarized and H becomes more ionizable, more acidic than in the bulk solvent. This is similar to the effect of an electronegative central atom in an oxyacid such as H,SO, 24.71 (a) Both compounds have the same general formulation, so Co is in the same (+3) ‘oxidation state in both complexes. (©) Cobalt!) complexes are generally inert; that is, they do not rapidly exchange ligands inside the coordination sphere. Therefore, the ions that form precipitates in these two cases are probably outside the coordination sphere. The dark violet compound A forms a precipitate with BaCi,(aq) but not AgNO,(aq), so it has SO, outside the ‘coordination sphere and coordinated Br, [Co(NH,) [Cd(en),}*(aq) + 4CH,NH,(aq) = 23.5 kd AG* =-RTInK,,; -23.5kJ =-2.35 « 10" -2.35 x 108 J = 85144 x 298 K x In Ky, In Ky, = 9.485, K,, = 1.32 x 104 Kemol ‘The magnitude of K,, is large, 80 the reaction favors products. The bidentate chelating ligand en will spontaneously replace the monodentate ligand CH,NH,. This is an illustration of the chelate effect. Using the stepwise construction from part (a), DH? = 57.3kJ-56.5kJ=0.8kd AS® = 67.3.JK + 14.1 JK = 81.4 JK TAS = -298 K x 81.4 JIK = -2.43 x 104 J = -24.3 kJ The chelate effect is mainly the result of entropy. The reaction is spontaneous due to the increase in the number of free particles and corresponding increase in entropy going from reactants to products. The enthalpic contribution is essentially zero because the bonding interactions of the two ligands are very similar and the reaction is not ‘downhill in enthalpy. ‘AH® will be very small and negative. When NH, replaces HO in a complex (Closer Look Box), the tighter bonding of the NH, ligand causes a substantial negative AH* for the substitution reaction. When a bidentate amine ligand replaces a monodentate amine ligand of similar bond strength, AH’ is very small and either positive (part (c)) ‘or negative (Closer Look Box). In the case of NH, replacing CH,NH,, the bonding characteristics are very similar. The presence of CH, groups in CH,NH, produces ‘some steric hinderance in [Cd(CH,NH,),J". This complex is at a slightly higher ‘energy than [Cd(NH,),°*, which experiences no steric hinderance, so AH” will have ‘a negative sign but a very small magnitude. Relief of steric hindrance leads to a very ‘small negative AH” for the substitution reaction. 62524 Coordination Compounds Solutions to Exercises 24.73 24.74 24.75 First determine the empirical formula, assuming that the remaining mass of complex is Pd. 37.69 8r * Fe gorg pe 04708 mal Br; 0.4706/0236 2839C * ens 356 mol C; 2.356/0.2361 = 10 6.60gN SaoTgHl = 0.4711 mol N; 0.4711/0.2361 = 2 2379H =awend = 2.351 mol H; 2.354/0.2361 = 10 25.199Pdx = 0.2361 mol Pd; 0.2361/0.2361 = 1 The chemical formula is [Pd(NC,H,),Br,]. This should be a neutral square-planar complex of Pd(ll), a nonelectrolyte. Because the dipole moment is zero, we can infer that it must be the trans-isomer. D Determine the empirical formula of the complex, assuming the remaining mass is due to ‘oxygen, and a 100 g sample. 10.0gMn x pT = 0.1820 mol Mn; 0.182 / 0.182 286gK x me = 0.7315 mol K; 0.732/0.182=4 B8gC x rs = 0.7327 mol C; 0.733 / 0.182 = 29.29Br x Taree 0.3654 mol Br; 0.365 / 0.182 = 2 23490 mango = 1.463 mol O; 1.46 /0.182 = 8 ‘There are 2 C and 4 O per oxalate ion, for a total of two oxalate ligands in the complex. To match the conductivity of K,[Fe(CN),], the oxalate and bromide ions must be in the coordination sphere of the complex anion. Thus, the compound is K,[Mn(ox),6] (2) __ The reaction that occurs increases the conductivity of the solution by producing a greater number of charged particles, particles with higher charges, or both. Its likely that H,O from the bulk solvent exchanges with a coordinated Br ~ according to the reaction below. This reaction would convert the 1:1 electrolyte, [Co(NH,),Br,]Br, to 1:2 electrolyte, (Co(NH,),(H,0)Br]Br. 62624 24.76 24.77 Coordination Compounds Solutions to Exercises (b) [Co(NH,),8r,]"(aq) + H,O(!) > [Co(NH,),(H,0)Br]"(aq) + Br(aq) (©) _ Before the exchange reaction, there is one mole of free Br~ per mole of complex. mol Br- = mol Ag* M= moll; L AgNO, = mol AgNO,/M AgNO, 3.87 gcomplex , _1mol complex _Lmolcomplex_ x 0.02500 L soln used = 0.500L son 366.77 gcomplex 5.276 « 10“ = 5.28 x 10“ mol complex 5.276 x 10% mol complex x —1T0IBr__, 1molAg” , _1LAg (aq) 1molcomplex — 4 mol Br 0.0100 mol Ag "(aq) = 0.05276 L = 52.8 mL AgNO,(aq) (3) After the exchange reaction, there are 2 mol free Br- per mol of complex. Since ‘M AGNO,(aq) and volume of complex solution are the same for the second experiment, the titration after conductivity changes will require twice the volume calculated in part (c), 105.52 = 106 mL of 0.0100 M AgNO,(aq). Calculate the concentration of Mg** alone, and then the concentration of Ca’* by difference. Mx L=mol 0.0104 mol EDTA, 9 o4g7, x 1moiMg 1 {mol EDTA 0.0104 M EDTA x 0.0315 L = mol (Ca + Mg™) 0.0104 M EDTA x 0.0187 L = mol Mg” (0.0104 M EDTA x 0.0128 L = mol Ca" 1molCa?" , 40.08gCa* , 1000mg , 4 TmolEDTA "4 mol Ca 9 0.100LH,0 (0.0104 M EDTA x 0.0128 L x = 53.35 = 53.4mg Ca" 18210) Amol mol 6.022 x 10 molecules = 3,022 x 10° = 3.02 x 10°" J/photon, BE = hy = 3.02 « 10°""J; v= Eh v= 3,022 * 10° JI6.626 x 10™ Jes = 4.561 x 10"= 4.56 x 105“ 2.998 x 10° m/s 4.561«10"s 7 = 6.57 x 107 m=657 nm We expect that this complex will absorb in the visible, at around 660 nm. It will thus exhibit a blue-green color (Figure 24.25). 62724 Coordination Compounds Solutions to Exercises 24.78 24.79 ‘The process can be written: H{g)+2e > 2H"(aq) E45 = 0.0V Cus) > Cu +26 Eg = 0.337V (Cu*(aq) + 4NH,(aq) > [Cu(NH,)d* (aq) ==? H,{g) + Cu(s) + 4NH,(aq) 2H"(aq) + [Cu(NH,),P"(eq) B= 0.08 V *Prcuney21 E=E*-RTInK, K,2 1! une Py, INH atm, [H'] = 1 M, [NH] E=E°-RTin(1), E=E°*-RT(0); E=E*=0.08V Since we know E” values for two steps and the overall reaction, we can calculate “E™ for the formation reaction and then K,, using E 0882 log K, for the step. M, [Cu(NH,),P* = 1M, K=1 Evy = 0.08 V = 0.0V- 0.337 V+ * °E;" =-0.08 V+ 0.337 V=0.417V=0.42V 0.0592 = ME) _ 200.417) ny (OBK: WOOK o o502 ~ “O.0502 10%" = 4.2 x 10% 14.0878 = 14.09 (2) The units of the rate constant and the rate dependence on the identity of the second ligand show that the reaction is second order. Therefore, the rate-determining step cannot be a dissociation of water, since that would be independent of the concentration and identity of the incoming ligand. The alternative mechanism, a bimolecular association of the incoming ligand with the complex, is indicated. (b) _Therelative values of rate constant are a reflection of the kinetic basicities of the three ligands: Pyridine > SCN > CH,CN. (©) Ru(lll) is ad*ion. Inalow-spin d° octahedral complex, there is one unpaired electron, 628