KiputdA MERcjuNng Bestion of Knowledge (Constituent College of Mol Unversity) SCHOOL OF SCIENCE, TECHNOLOGY AND ENGINEERING DEPARTMENT OF CHEMISTRY AND BIOCHEMISTRY ‘COURSE TITLE: Coordination Chemistry COURSE CODE: CHE 318 SEMESTER: " Credit hours: 3 Course Purpose The purpose of this course is to equip learners with development and theories of coordination chemistry Objectives The objectives of this course are to: a) To Introduce learners to structure and isomerism of coordination compounds b) Provide the leamers with knowledge in reaction mechanism in inorganic chemistry Expected Learning Outcomes At the end of this course, learners should be able to: 1. Describe the structure and isomerism of co-ordination compounds 2. Explain reaction mechanisms of inorganic chemistry 3. Describe the bonding theories of metal-ligand bonds Course Content Introduction: Coordinate bond, electronic configurations of d-block elements, Hard and soft acids and bases (HSAB) concept and their applications. Development of co- ordination chemistry; Blomstrand-Jorgensen and Werner's theories. Coordination number and geometry. Ligands. Nomenclature, structure and isomerism in co-ordination compounds, Rates and reaction mechanisms of inorganic chemistry: Brief survey, lability and inertness, substitution-octahedral and square planar (trans effect), Dissociative, redox or electron transfer, Theories of metal-ligand bonding, Preparation and stability of co-ordination complexes. Applications: Monodentate and multidentate, chelating agents and bioinorganic. Dr. Magero Denis CHE 318 Alupe University College 1 Scanned with CamScannerLearning and Teaching Methods Lecture, Practical, Discussion, Exercises, Tutorials. Course Assessment Type Weighting (%) Examination 70% Continuous Assessment Tests 30% Total 100% Instructional Material / Equipment Chalk and Chalkboard, Pen/whiteboard, Power Point/LCD Course Text / References 1. Cotton, F. A. and Wilkinson, G. (1988). Advanced Inorganic chemistry, 5" Edition Wiley Interscience. Kettle, S. FA. (1988). Physical Inorganic Chemistry; Coordination Chemistry Approach. Oxford university press. Housecroft, C. E. (2001). Inorganic Chemistry. Prentice Hall. Huheey, J. , Keiter, E. A. and Keiter, R.L. (1993), Inorganic Chemistry: Principles of Structure and Reactivity, 4" Edition, Mapper Collins. . Shriver, D. F., Atkins, P.W. and Lengford, C. H. (1990). inorganic Chemistry. ELBS, Oxford Course Lecturer: Dr. MAGERO Denis Signature: Meyeies Date: 21/02/2022 Scanned with CamScannerINTRODUCTION What is coordination Chemistry? Itis the study of co-ordination compounds. {co-ordination compound consists of a central metal ion bonded to a neutral or negatively charged species with lone pairs of electrons through co-ordinate bond, Examples include: [Cu(NNH3j}** and [Cocl,y? Coordinate covalent bonds are the covalent bonds in which both the bonding electrons are contributed by one of the bond partners. ener ‘The central metalion must have empty orbitals to accommodate/accept electrons donated by the neutral or negatively charged species, The neutral or negatively charged species that donates electrons to the central metal ion is called aligand, ‘Transition metals form co-ordination compounds because they have pattially filled d orbitals which can accept electrons from the ligands. A transition metal is one that has partially filled d orbitals in atomic or ionic state The chemistry of transition metals can be described in terms of Lewis-acid Lewis-base reaction, ‘The central metal atom orion acts as a Lewis acid by accepting electrons while the ligands act as Lewis base by donating electrons, HARD-SOFT ACIDS AND BASES Hard Acid ‘Small, compact, highly charged electron acceptor. Hard Base Small, highly electronegative electron pair donor. Soft Acid, Soft Base Large, highly diffused and easily polarizable species HARD ACIDS THRO BASES SOFT ACIDS SOFT BASES A ea Na’, ADs, NHs, H20, F,, Br, O7, Ca", Ag’, Au, Pd®, CN, CO, 1, SCN eT ja He? Or. Magero Denis CHE 318 Alupe University College 4 Scanned with CamScannerHSAB RULE Hard acids preferentially bind with hard bases while soft acids bind with soft bases Transition Metals At ransition metal has partially filled d-orbitals in atomic orionic state. There are four series of the d-block transition metals namely 3d, 4d, Sd and 6d series 3d-series ~ Se (21) - Zn (30) Ad-series ~ Y (39) ~ Cd (48) 5d-series ~ La (57) - Hg (80) 6d-series ~ Ac (89) — Mt (109) Electronic Configuration of Transition Metal Pauli Exclusion Principle In an atom, no two electrons can have the same values of the four quantum numbers. An orbital can accommodate a maximum of two electrons and should have opposite spin. Hunds Rule ‘When electrons enter subshells (orbitals) with the same angular momentum quantum number (|) in agiven shell they do so singly before pairing begins. Aufbau Principle Electrons fill or enter orbitals systematically starting with the lowest energy orbital. wis 22s 2p 3s 3p 3d 4s 4p 4d 4f _5s 5p 5d nce Ul) 7s Exercise 1. Write down the electronic configuration of all the elements in 3d and 4d series of the transition metal elements. Write down the electronic configuration of the following ions/atoms. Tit22), Cr(24), V(23), Mn(25), Cu(29), Cr°*(22), Co*(25), V5"(18), Fe** (24), Ni?*(26), Ag!" (46) Dr. Magero Denis CHE 318 Alupe University College 2 Scanned with CamScannerProperties of Transition Metals 1. They form co-ordination compounds/complexes, 2. They form coloured salts. The wavelengths of light associated with electronic transitions in transition metals fall within the visible region of the electromagnetic spectrum, 3. They have got variable oxidation states e.g, Mn from 42+ +7 ie, from n-1 d orbitals and ns orbitals 4. They act as catalysts because of the variable oxidation states. d-orbita s There are 5 types of d-orbitals depending on the distribution of their electron densities along the Cartesian plane. These are; day dhe, ya, diy? ds? The day dy and dy; have their lobes distributed between the axes, ie. The d,+,’ and d,” have their lobes distributed along the ayes, ie. Effective Atomic Number (EAN) This is the number of electrons in a central metal ion or atom plus those gained from the ligands. Each ligand contributes/donates 2 electrons to the central metal atom/ion. Central metal ions in octahedral complexes would prefer to have an EAN equals to the atomic number of the nearest noble gas. Example a) Calculate the EAN of the metal ions/atoms in the following compounds i Fe(COn, ii, (Co(NHsi)"* Dr. Magero Denis cHe 318 Alupe University College 6 Scanned with CamScannerih [Cr(H,0),* Solution a) Oxidation state of Fe = 0 No of electrons in Fe = 26 Electrons from the ligands = EAN of Fe in Fe(CO), = 26 + 12 x6=12 8 b} Oxidation state of Co = +3 No of electrons in Co™ = 24 Electrons from the ligands = 2 x 6 = 12 EAN of Fe in Co** in [Co(NHs)g]”* = 24 + 12 = 36 Historical Development of Co-ordination Compounds Alfred Werner studied and explained the structure of co-ordination compounds more than anybody else. The first compounds to be studied were Cobalt ammoniate chlorides. It was discovered that when air was bubbled through a solution of CoCl, and ammonia, a reddish-brown precipitate was formed. The composition of the product was found to be Cobalt, CoCl,6NH3 Ox(oxidation) CoCIa0q) + NHyaq) ~~ COC. 6N 309) Later, it was found that it was possible to replace some ammonia molecules in the above compound to form the following compounds; CoCI, SNH3, CoCl;4NH; and CoCl;.3NH3 The compound formed also showed different properties in solution eg, it was found that the compounds showed different conductivities in solution and precipitated different number of moles of chloride ions in presence of silver nitrate. The properties of the compounds are summarized as shown in the table below; Compound Conductivity No. of moles of CI’ ions Precipitated from one mole of the compound “CoC, 6NH; | High 3 (All CI'ions precipitate) CoCl,SNH3 Moderate 2 7 CoCl.4NH; Low 1 _ CoCh,3NHs - Low 0 - Conductivity of a compound in solution will depend on the number of ions produced when the compound ionizes in solution. Scanned with CamScanner‘The more ions produced by a compound in solution, silverions in solution, CI ions precipitate as follows: + Bes ipitate, Agihagy + laa * A9Cleay(white precip ) From the above observations, Alfred Werner came up with the following ideas to explain the structure of co-ordination compounds. i. Acentral metal ion i.e. Co will have two valencies namely primary and secondary valencies. The primary valency of the central metal ion is its oxidation state and is satisfied by negatively charged ion. Secondary valency is the co-ordination number of the central metal ion and is satisfied by a neutral molecule/negatively charged ion. ii. co-ordination compound had two parts, ie. inner sphere (co-ordination sphere) and the outersphere. Inner sphere: consisted of the central metal ion and the neutral molecules or anions which satisfy the secondary valency or the co-ordination number of the central metal ion, Ions in the co-ordination sphere did not ionize the solution. Outer sphere: consisted of the counter ions which satisfy the primary valency of the central metal ion. iii, For a given metal ion, the secondary valency was fixed in a given oxidation state. In his presentation of the structure of co-ordination compounds, ligands which satisfy the primary valency of a compound were represented using solid lines while those ones satisfying secondary valency were represented using dotted lines. Primary valency Secondary valency One of the chloride ions satisfies both primary and secondary valencies. The chloride ion which satisfies both primary and secondary valencies is inside the co-ordination sphere and will not ionize the solution CoCls.SNHs Scanned with CamScannerCoCl;.3NH3, Modern way of representing the formula of a co-ordination compound The ligands satisfying the secondary valency and central metal ion which are inside the co- Ordination sphere are put inside {_] while the ions satisfying only the primary valency are put outside the brackets. Using the Cobalt ammoniate chloride to illustrate the modern way of writing the formula of a co-ordination compound, the ammoniates will have the following formulas. Formula lonization Products No. of ions CoCls.6NHs [Co(NHs}e]Cls [Co(NHs)el** + 3Cl aq) 4 CoCls.SNHs [Co(NH3)sCI]Chr [Co(NHs)sCl}®* + 2Cliaa) 3 CoCls.4NH3 [Co(NH3) Tridentate Ethylenediamine (en) EDTA (ethylenediaminetetraacetic acid) Hexadentate a ze CHC, Pm, of Sa ncn . a None oc 7 3 ¢) Bridging verses chelating ligands ie. M = Ligand M M,~&— HoN—cH,CH,—NH;$— = M A bridging ligand binds itself simultaneously to two metal centres ie. it links two metal centres Scanned with CamScannerChelating ligand binds itself to one metal centre via two donor atoms simultaneously forming ring structure around the metal centre €.9. Diaminopropane Mi 6 membered ring 4) Ambidentate ‘An ambidentate ligand can use more than one type of donor atom to bind to a metal centre depending on experimental conditions and metal ion e.g. NO, CN, SCN NOMENCLATURE OF CO-ORDINATION COMPOUNDS (IUPAC) Co-ordination compounds are named according to IUPAC rules. Ligands Neutral Ligands Some neutral ligands have special names e.g. FNH3 amine CO carbonyl NO nitrosyl HO aqua Anionic Ligands Names end with suffix CI chloro F fluoro 1 iodo CO,?' carbonato SO,” sulphato 0? oxo 0," peroxo NO; nitro S? sulphido CN cyano SCN thiocyanato CHsCOO acetonato Scanned with CamScanneracac- acatylacetonato Oxolato (ox) The ligands are listed alphabetically If the ligand is ambidentate, the co-ordinating/donor atom is shown ie. NOz (N= nitro) ONO (0= nitro) SCN (S- thiocyanato) CNS (C- thiocyanato) Ifa ligand appears more than once in a complex, the prefixes di tri, tetra, penta, hexa are used to indicate the number of ligands. Ifthe prefix appears in the ligands, a different system is used i.e. the prefixes bis (2), tris (3), teterekis (4), pentakis (5), hexakis (6) etc. are used. Bridging Ligands Symbol is placed before the Metal lons The oxidation state of the metal ion is indicated using roman numbers put in brackets 0. If the complex is anionic e.g. [Zn(OH),]”,the name of the metal centre ion ends with the suffix ‘ate’ Zine Zincate Chromium, Chromate Manganese Manganate Platinum Platinate Nicket Nickelate Scanned with CamScannerCopper Cuprate Ferric Ferrate Ferrous Ferrate Vanadium Vanadate Metal Complex Ligands are named first followed by the metal ion or metal centre. Mf co-ordination compound consists of cationic and anionic complex ions, the cationic part is named first. Examples Give IUPAC names of the following compounds. [Zn(OH),)* Tetrahydroxozincate (II) ion [Co (NH3)¢ Chy"CI Tetraaminedichlorocobalt (lll) chloride Cobalt (lll) amine chloro ie3+(2=H1 [Cr(en)NO,F}"NOs" bisethylenediamineflouro N-nitro chromium (ill) nitrate ENE en (ethylenediamine) [Ni EDTA) Ethylenediaminetetraacetonato Nickel (IV) Na’ [Al(OH).) Sodium tetrahydroxo aluminate (II!) [Ag(NHs)2]*{Min(H20);Cla} Diaminesilver (\) tris aqua trichloro manganate (!!) Exer Name using the IUPAC rules the cobalt and platinum ammonate chlorides previously discussed in class. Bridging Ligand H 2 fo) \ cote Fe(NHs)q [SOx uo” U H Bisethylenediammine cobalt (I)-di-p-hydroxotetraammine iron (I) sulphate H + N. (HaN) 6 are rare but can occur in large metal ions ie Lanthanides and actinides elements. ISOMERISM IN CO-ORDINATION COMPOUNDS Isomers are compounds with the same chemical composition but different arrangement of their constituent atoms. Since their atoms are arranged differently, isomers are different compounds with different reactivity and different physical properties (such as colour, melting and boiling points, and solubility). Isomerism Ionization Hydrate Linkage Coordination Coordination position Ligand Polymerization ee ell Optical _| Structural Isomerism TYPES ‘A. GEOMETRIC ISOMERISM Co-ordination compound can have cis and trans isomers depending on the spacial arrangements of the ligands relative to the central metal ion e.g. [PtNH3)2Cla) 1 IH CN Pt: H, nO ch st Trans-[PU(NH3),Cla} Hh Ns N a et Cis-{PtiNHy)2Ch] B. IONIZATION ISOMERISM This type of isomerism exists in co-ordination compounds which have the same composition but give different ions upon ionization in solution, Scanned with CamScannerind inside the co- This is brought about by the interchange of ligands outside a ordination sphere e.g. NH3 + Br NH3 Co. HN | ™ bw | ~e Han HN [Co(NH3)sCJBr [Co(NH3)s6r]C! OR {Co(NH3)sCl]SO, and [Co(NH;)SO,]CI [Co(NH3)5CI}SO,4¢aq) > [Co(NH3)5ClI fst + SO%aq) [Co(NH3)5$04]Cl(aqy > [CO(NH3)sS04 Ifaq) + Cleaqy C. CO-ORDINATION ISOMERISM Itis possible to have a co-ordination compound that consists of two co-ordination spheres one being an anion and the other one being a cation. In co-ordination isomerism, the ligands are interchanged between the two co- ordination spheres e.g. [Co(NHs)c}**[Cr(CN)e]* and [CO(CN)«] [Cr(NH3)c] D. CO-ORDINATION POSITION ISOMERISM This type of isomerism occurs in complexes with bridging ligands. The two isomers will have different compositions of the ligands around the metal centers e.g. oO H, (HgN)4Co. (Co(NHg)2Cl | Clr Ny, Oo H And oO aN Me Vue Cly oO H E. LIGAND ISOMERISM This type of isomerism occurs in complexes or co-ordination compounds whose ligands are isomers e.g Scanned with CamScanner[Co(NH2CH2CH2CH2NH>)2CI,]Cl And {Co(NHCH,CHNH,)2Ch]CI CHs F. HYDRATE ISOMERISM This type of isomers have different compositions of water molecules outside and inside the co-ordination sphere e.g. [Cr(H20)¢]Cls 3cr [Cr(H20)sCI}Clz.HO 2cr [Cr(Hz0).Cl,}C1.2H.0 cr G. LINKAGE ISOMERISM This type of isomerism is shown by complexes with ambidentate ligands. The wo isomers will have the same composition but will be linked via different donor atoms in ambidentate ligands. ‘The donor atom to be used for bonding in an ambidentate ligand will depend on the experimental conditions and the nature of the metal ion e.g. For thiocyanato ligand SCN, Zinc ion will prefer to bond via sulphur while mercury will prefer the nitrogen linkage. dilute Nis [Co(NH,)sCIC 3 [Co(NHs)s(H20)]Cls NaNO, NaNO>. conc. HCl dilute HC 1 [Co(NH,);ONO]Cl, > — [Co(NH3)sNO2]Cly H. OPTICAL ISOMERISM This isomers rotate in the plane polarized light in different directions. The isomers will have a chiral centre and will be mirror images of each other e.g. [Co(NH2CH2CH2NH2)2Cl2]Cl Exercise 1. Indicate the types of isomerism exhibited by the following coordination complexes and draw the structures for these isomers. i. K{Cr(H20)2(C20.)2) ii, [Co(en)3}Cls ili, [CO(NH3)s(NO2)](NO3)z iv. [Pt(NH3)(H20)Cl.) Scanned with CamScannerJES OF CO-ORDINATION COMPOUNDS BONDING THEORI ompounds namely There are 3 bonding theories of co-ordination ¢ Valence Bond Theory (VBT) Crystal field/ligand field theory (CFT) or (LFT) Molecular Orbital Theory (MOT) i) ii) iii) i) Valence Bond Theory (VBT) is acit i as Lewis This theory considers the central metal ion as a Lewis acid and the ligands bases. | Bonding in the complex is as a result of overlap of empty orbitals of the centra metal atom with field orbitals of the ligands. : Before the orbitals overlap, the valence shell orbitals of the central metal atom will undergo hybridization and the type of hybrid orbitals formed will depend on the geometry of the cental metal atom/ion ie. Geometry Type of hybrid orbitals Tetrahedral sp* “Square planar _| d’sp (inner orbital complexes) ie. (n-1) d?ns np/low spin complexes spd? high spin complexes/outer orbital complexes Octahedral spd? (outer orbital complex / high spin OR dsp? (inner orbital complex / low spin complexes) Electrons of the central metal atom occupying the valence orbitals will not participate in bonding but determine the magnetic properties of the complex. Recall Magnetic moment spin = nu ¥ 2) Where n = number of unpaired electrons, units BM (Bohr Magnetons) Octahedral Complexes The complex [Cr(NHs).]°* is octahedral and paramagnetic with 3 unpaired electrons. Account for this observation using the valence bond theory (Cr = 24) Solution Oxidation state of Chromium in the complex is +3 Electronic configuration of Cr?* = [Ar]3d3 45° {tT 3d 4s 4p lon-bonding electrons Scanned with CamScannerHybridization LAT 3d In the complex (CrNH)¢)*° [Ar]] bP RL | x Proc XK vc | x« [J | ) 3d as ~ Pp . X~ electrons from the ligands Example 2 The complex [Fe(H;0),)°* is octahedral and paramagnetic with 1 = 4.89 BM. Account for the observation using VBT. (Fe=26) Solution Oxidation state of Fe in the complex is +2 Electronic configuration of Fe = [Ar]3d°4s* Fe?" = [Ar]3d°4s° tar] AFLP TELE | 3d 4s 4p Water is weak field ligand so there is no pairing of electrons in 3d orbital iron in ‘octahedral environment. Since the complex has 4 unpaired electrons, the electrons in the 3d orbitals of Fe?” are not perturbed/disturbed before or during bonding. This means the central metal ion uses outer d-orbitals for bonding ie far] fk LATE I ETE 3d 4s 4p a Hybridization tar] AFT ETE LATA vx] [ex [oe J xe vx | xe 3d to 4p 4d sp°d Magnetic moment spilt = n(n + 2) = [4(4 + 2) = 4.89 BM Assignment i) The complex [Fe(CN).]* is octahedral with 1 unpaired electron or paramagnetic with p, = 1.75 BM. Account for this observation using VBT. (CN isa strong field ligand) Solution In this complex, Fe is present as Fe” Scanned with CamScanner: 546° tarjad’4s? Fe? = (Ar)30°s Electronic configuration of Fe = far) [TELE DAE 7 3d 4s i rbitals pair up Because CN‘is a strong fi dof p fAr] NENA IE 3d ield ligand, electrons in 3. 4s 4p Hybridization [Ar] Xt} NEL 3d dsp? The complex FeF,* is octahedral with 5 unpaired electrons. Account for this =26) ii observation using VBT. Solution Oxidation state of Fe in the complex is +3 Electronic configuration of Fe = [Ar]3d°4s? Car] LF TET TET 3d 4s Since F is a weak field ligand, the electrons in the 3d orbitals of Fe** are not perturbed/disturbed before or during bonding. This means the central metal ion uses outer d -orbitals for bonding i.e, Fe®* = [Ar]3d°4s°, that’s; 4p In the complex, far] FTE TET TE 3d Tetrahedral Complexes The complex (CuCl,]” is tetrahedral and Paramagnetic with p, = 1.73 BM. Account for this observation using VBT. (Cu=29) Solution Oxidation state of Cu in the complex is +2 Electronic configuration of Cu = (Ar]3d"*4s' Cu? = [Ar]3d%4s° Scanned with CamScannerth TT Trt 3d as 3 In the complex, a TAKEN RTE) ff] ee 3d as ap Using VBT account for the observation that the complex [Ni(CN)al” is tetrahedral and paramagnetic with 2 unpaired electrons. (Ni =28). Square Planar Complexes The complex [NiCl,)* is tetrahedral and paramagnetic. Account for this observation using VBT. (Ni=28) Solution Oxidation state of Niin the complex is +2 Electronic configuration of Ni?" = [An]3d* tei OC) CL 3d as 4p In the presence of weak field Cl’ ligands, NO pairing of electrons occurs eT 3d In the complex rd EEE) od debe 3d 4s 4p The complex [Cu(NHs]4]*" is square planar complex. Advantages of VBT 1. The theory can be used to account for the magnetic properties of complexes. 2. Arelatively simple theory. 3, Itcan be used to predict the geometry of a complex Disadvantages 1. Cannot account for the spectral properties of complexes because d-orbitals are degenerate. Cannot explain why a metal ion prefers a certain geometry. Cannot explain why some complexes are more stable than others. Scanned with CamScanner‘ ion in complexes. 4. It cannot explain for distortion in / / 5, It assumes that bonding between central metal ion and ligands is purely covalent. This is not true as complexes have been shown to exhibit ionic properties. What is spectrochemical series? Explain the difference between a weak field ligand and a strong field ligand. Solution The arrangement of ligands in order of their increasing field strengths, /e, increasing crystal field splitting energy (CFSE) values is called spectrochemical series. I< Br < SCN’ < Cl < F< OH’ < ox < HO < EDTA* < NH; < en < CN’ P. (to be collected on 25" March 2022) Exercise 1. Explain on the basis of VBT that (INi(CN).]* ion with square planar structure is ion with tetrahedral geometry is Paramagnetic. diamagnetic and the [NiCl,J gnetic though both are 2. [NiCl.J* is paramagnetic while [Ni(CO)4) is diama tetrahedral. Why? 3. [Fe(H2O)s}*’ is strongly paramagnetic whereas [Fe(CN).}* is weakly paramagnetic. Explain. Scanned with CamScannerTHE CRYSTAL FIELD THEORY (CF The theory as: "y assumes that the bonding between the ligands and the central metal atom or ion is purely electrostatic. The ligands are considered to be negatively charged points while the metal centers are Positively charged. Ifthe ligand is neutral, it will be assumed to approach the central metal atom or ion via the negatively charged end H HN: —e H As the ligands approach the central metal ion/atom, they will be repelled by the d- big orbitals of the central metal atom and this will cause disturbance of the d — orbitals ie. d orbitals will no longer be degenerate. The perturbation of d-orbitals will be determined by: ‘+ Orientation in space of the d- orbitals. + Crystal field or geometry of the complex. Case 1 Octahedral Complexes In an octahedral complex, the ligands approach the central metal or ion along the x, y and z axes. Recall, di2,2 orbital and d,? have their lobes lying along the axes while dy, dra, dy, have their lobes distributed between the axes. As the ligands approach the central metal atom, d,2.y2 and d,’ orbitals are repelled more than the dy, dyz, dy orbitals since their lobes lie in the direction of the ligands. This means that dyzy2 and d,’ orbitals will be destabilized more than the others, ie., G2 Gaya = barry centre Ina spherical/uniform hypothetical field toy d-orbitals (degenerate) Scanned with CamScannerEnea A, or 10 Dg - The energy separation between the two levels The eg orbitals are repelled by an amount of 0.6 Ao The tag orbitals to be stabilized to the extent of 0.4 Ao. 2. (2 x 0.6) + 3 x -0.4) =0 Tetrahedral Complexes In a tetrahedral complex, none of the d - orbitals points in the direction of the ligands but dy, diz, dz come closer in doing so than the dyzyzand dZ orbitals. This means that the splitting of the d- orbitals in a tetrahedral complex will be a reverse pattern of that of an octahedral complex ren is smaller than oc Infact, Aten =4/9 Aoct = (50% Soa) Splitting of orbitals in a square planar .d from an octahedral array/arrangement by A square planar geometry can be obtaine removing completely the ligands along the z-axis. cess has an intermediate stage where the octahedral complex undergoes nal distortion). The also dy, and di. The pro distortion by having two long bonds and four short ones (tetrago overall effect of the process will be stabilization of the d,2 orbital and Scanned with CamScannerNy i Na Lh Octahedral geometry ‘Tetragonal distortion Sap Long stabilization Short stabilization Tetragonal distortion dye Octahedral ¥ Complete removal of ligands along x axis | a,b oy Asquare planar Octahedral Tetrahedral it dye distortion M Square planar Scanned with CamScanner »dgr—y? dey Eneegy Octaredzal Square plana Factors affecting the extent of splitting 1. Oxidation state of the central metal atom. Large oxidation state. Magnitude of A splitting increases with increase in oxidation state of the central metal atom. 2. Size of the metal/central metal atom/ion E.N.C The smaller the size/ion have large effective nuclear charge and will attract the ligands strongly. This will cause greater splitting of the d — orbitals in a complex. 3. Geometry of the central metal atom Recall that Aten =4/9 Aca (50%) buen is smaller than Agc because of the following reasons; i. In an octahedral complex, the central metal atom or ion is surrounded by 6 ligands as compared to four in a tetrahedral complex. More ligands will imply greater repulsion of the d - orbitals and hence larger A splitting In an octahedral complex, two orbitals have their lobes lying in the directions that the ligands approach the central metal atom while in a tetrahedral complex, none of the d~ orbitals lie in the direction of the ligands. Repulsion in octahedral complexes is greater than those of tetrahedral complexes 4, Nature of the ligands Different ligands will have different splitting Spectro chemical series arranges ligands according to the order of greater splitting Scanned with CamScannerr
> equitorial bonds L There will be greater electronic repulsion experienced by the ligands along the x and y axis than along the z axis. The cationic ionic distance along z-axis will be shorter than along x and y axis. The same effects of observation could be seen in d', d’, d? etc. in excited state. Jahn-Tellers distortion occurs in octahedral complexes with unsymmetrical filling of dio and d,22 orbitals and results in a complex either having two long bonds and four short bonds or four long bonds and two short bonds. Question Account for the following scientific observation. Fluorine-metal bond are equal in manganese [MnF.]* but in [CrF,]* four bonds are short and two are long ones. (Cr=24, Mn Solu Mn electronic configuration = (Ar]3d°4s? ; fluorine is a weak field ligand jn Mn?* [Ar]3d°4s° Scanned with CamScannertoa, dp day2 A 4 t dy G2 4, 78 In [MnF,}*, the bonds are not at equidistance because there is no Jahn-Teller distortion, ie. eg orbitals are evenly filled. Cr (24) E.C. = [Ar]3d%4s" cr = [Arj3d*4s° ao, G2 Gaya ee \ oy de a. 78 The eg orbitals are unsymmetrically filled and it undergoes Jahn-Teller distortion. Advantages of Crystal Field Theory 1. Accounts for spectral and magnetic properties of metal complexes 2. Explains why some complexes are more stable than others ie. CFSE values 3. Can account for distortions Vahn-Teller distortions) in complexes. Disadvantages of Crystal Field Theory 4. The central metal. Assumes central metal ion/atom uses only electrons from the d-orbitals for bonding which is not true. 2. Assumes the metal-ligand bond is purely ionic. This is not the case as some evidence has shown presence of covalent characters in metal-ligand bonds. One evidence of covalent character in metal complexes is the nephelauxetic effect. This is the expansion of the d-orbitals of the central metal ion in the presence of ligands. ‘The expansion comes about because as they overlap to form covalent bonds. 3. Cannot account for the formation of rt bonds in metal complexes. MOLECULAR ORBITAL THEORY According to this theory, the orbitals of the central metal atom will overlap with those of the ligands to form bonding and anti-bonding molecular orbitals. Scanned with CamScannerSome orbitals of the central metal ion will not participate in bonding and these orbitals are called non-bonding orbitals (tz) The molecular orbital energy level diagram of a co-ordination complex or compound resulting from overlap of atomic orbitals of the ligands and the central metal ion in an octahedral complex can be represented as below. ag Orbitals on metal Molecular orbitals, Ligand group orbitals Atomic Orbital Molecular Orbital 4s + ligand (1) 4p + ligands (3) 3d (diz,y2and d,2) + ligands (2) Question Account using M.O theory that the complex [Co(NH;]«]* is octahedral and diamagnetic. Solution Co* [Ar]3d° Total number of electrons in the complex will be: 6 + 12 = 18 e's Scanned with CamScanner{Fe(H,0),]”*. Using MOT, account for the fact that this complex is octahedral and paramagnetic with four unpaired electrons (weak field). Fe® [Ar]3d%4s? Fe’’ [Ar]3d° What are the similarities between MOT and crystal field theory? To be collected on 25" March 2022 ELECTRONIC TRANSITION OF CO-ORDINATION COMPOUNDS Electronic transitions in metal complexes occur between the e, and ta orbitals. The spacing between the orbitals have energies whose wavelengths fall within the visible region of the spectrum and this explains why most transition metal complexes are coloured. So the colour of a complex will depend on the wavelength of 4 splitting which depends on a number of factors such as geometry of the complex, nature of the ligands and oxidation state of the central metal ion, Electronic spectra of metal complexes will be useful in understanding the bonding and the structure of metal complexes, Scanned with CamScannerTypes of Electronic Transitions a) Intra Ligand electronic transitions / This transitions occur within the ligand molecular orbitals e.g. non 030" nant The position of the bands of intra-ligand transitions will change if the ligands are substituted in a molecule. b) d-d transitions This transitions occur between the d orbitals ©) Charge transfer transitions Ligand to metal charge transfer (LMT) transition - metal must have a high oxidation state and empty d orbitals. Metal to ligand charge transfer (MLCT) transition - Low oxidation state metal ion. Ligand must have empty orbitals. Special feature in an electronic spectrum 1. Number of peaks Number of peaks in an electronic spectrum will depend on the electronic configuration of the central metal ion e.g. d', d?, d® and d* complexes — one band or peak expected d° complex — many low intensity peaks @, d?, d’ and d® complexes - Three bands or peaks expected Two diagrams Orgel diagram Tanabe-Sugano diagram 2. Position of the peaks Appearance at high wave numbers means a large spacing, Positions of the peaks depend on the A splitting. If they appear at higher wave numbers, splitting between the d — orbitals is large 3, Intensity of the peaks Are they low or high intensity peaks? Measured in terms of absorbance. Azecl «=(4) Intensity of the peaks will depend on the allowedness of the transition. Scanned with CamScanner