Chapter 20 - d-block metal chemistry - …

1 1 Chapter 20 d- block metal chemistry :coordination complexesBonding: valence bond, crystal field theory, MO Spectrochemical seriesCrystal field stabilization energy (CFSE)Electronic SpectraMagnetic Propertiesfive d-orbitals and the shapes2 Hybridization schemes for the -bonding frameworks of different geometrical configurations Limitations of VB Theory3d4s4pVacant orbitals available to accept ligand electronsCr(III)3dd2sp3 Vacant orbitals available to accept ligand electronsFe(III)3dd2sp3 For Fe(III), the two d orbitals in the sp3d2hybrid orbitals would need to be from the 4d orbitals, which is not favorable because the 4d orbitals are much higher in energy than the 3d +rM-LSpherical Shell of e- density at rM-LMn+ 12 e-Crystal Field Theory (CFT)Crystal Field Stabilization Energy (CFSE) oo53252343dThe electronic absorption spectrum of [Ti(OH2)6]3 in aqueous of octfor some d- block metal trend in values of octfor the complexes [M(NH3)]

2 6]3 where M = Co, Rh, strength increases as one proceeds down a (II) < Ni(II) < Co(II) < Fe(II) < Cr(III) < Co(III) < Ru(III) < Mo(III) < Rh(III) < Pd(II) < Ir(III) < Pt(IV)Factors affecting the CFSEF irst, note that the pairing energies for first-row transition metals are relatively , the difference between strong- and weak-field, or low and high- spin cases comes down to the magnitude of the crystal field splitting energy ( ).1. Geometryis one factor, ois large than tIn almost all cases, the t is smaller than P (pairing energy), complexes are always weak-field (high spin)Square planar complexes may either be weak- or Oxidation State of metal Cation A greater charge on cation results in a greater magnitude of Why? A greater charge pulls ligands more strongly towards the metal , therefore influences the splitting of the energy levels Size of the metal Cation For second and third-row transition metal ions, ois larger than steric hindrance between the ligands better overlap are the other factors affecting the CFSE?

3 4. Identity of the ligands. A spectrochemical series has been developed and sorted by the ability to split metal < Br-< S2-< Cl-< SCN-< NO3-< N3-< F-< OH-< C2O42-< H2O < NCS-< CH3CN < py (pyridine) < NH3< en (ethylenediamine) < bipy(2,2'-bipyridine) < NO2-< PPh3< CN-< CO As the ligands decrease in size, their ability to split the d-orbitals increases. The larger and bulkier ligands exhibit more steric hindrance and approach the metal less might expect that ligands with a negative charge might split the d-orbitals better, but this is not always the case. Notice that water is higher in the series than OH-, even though O on OH-has a high concentration of charge. The dipole moment of H2O is larger than NH3, but NH3is higher in the series. PPh3is high in the series, but also very bulky, neutral and has a small dipole of the 3dorbitals in weak and strong field Fe3 (d5) crystal field stabilization energies (CFSE) for dnconfigurations; pairing energy, P, terms are included where appropriateHigh Spin : o < P Low Spin : o> PCFSE = E = Eligand field Eisotropic fieldPairing energies for some 3d metal ions**Pairing energy values refer to free ion, and may be 15-30% smaller for the complexed ion.

4 Orgel, J. Chem. Phys. 1955, 23, (cm-1)d4Cr2+20,425Mn3+25,215d5Cr+17,687M n2+23,825Fe3+29,875d6Mn+14,563Fe2+19,150 Co3+23,625d7Fe+17,680Co2+20,800 Using these pairing energy data and O, determine if the following complexes are predicted to be high spin or low ) [Fe(OH2)6]2+b) [Fe(CN)6]4-8 Square PlanarJahn-Teller DistortionsFor octahedral coordination, susceptible species are d4, d9, and low spin d7in which 1 or 3 electrons occupy the Jahn-Teller Theorem states: "any non-linear molecular system in a degenerate electronic state will be unstable and will undergo distortion to form a system of lower symmetry and lower energy thereby removing the degeneracy" 9 The relationship between a tetrahedral ML4complex and a cube; the cube is readily related to a Cartesian axis set. Tetrahedral complexes are almost invariably high to the ruleRare example of a low-spin, distorted tetrahedral complex11 Complexes with no metal -ligand (eg) orbitalsMLp orbitalsFor example,OHHsp3Cl-p -type covalent interactionMetal-Ligand -bonding only13 MLd(t2g) orbitalsPPh3dC Op*Can these pinteractions explain some of the anomalies in the spectrochemical series?

5 Cl-pp-type covalent interaction14 metal -Ligand p-bondingA p-donorligand donates electrons to the metal center in an interaction that involves a filled ligand orbitals and an empty metal p-acceptorligand accepts electrons from the metal center in an interaction that involves a filled metal orbitals and an empty ligand +LEmpty d(t2g) orbitalFilled p orbital - +Yields a less polar M-L bond, resulting in diminished ligands that exhibit this type of bonding include hydroxide (OH-), oxide (O2-), halides (I-, Br-, Cl-). These ligands tend to be at the lower end of the spectrochemical ligandsMetal s and p orbitals which are involved in bonding have been to Ligand pbondsMn+LFilled d(t2g) orbitalEmpty d or p*antibonding molecular orbital + -Backbonding between a filledmetal orbital and an unfilledligand orbital has a greater polarity in the M-L bond and greater splitting of the ligands that exhibit this type of bonding include phosphines (PR3), arsines (AsR3), cyanide (CN-), and carbonyl (CO).

6 16p-acceptor ligands Ligand Group p-orbitals17 Describing electrons in multi-electron systems: L and ML p2)1(momentumangular Orbitalhll Orbital angular momentum has magnitude and 2l+1spatial orientations with respect to the zaxis ( the number of values of ml), vectorial summation of the individual l values is necessary (review Box ).ml= 2 +2(h/2p)ml= 1 +(h/2p)ml= 0 0ml= -1 -(h/2p))2/(6ph)2/(6ph)2/(6ph)2/(6ph)2/(6 phml= -2 -2(h/2p)lLm M p2)1(momentumangular OrbitalhLL Describing electrons in multi-electron systems: S and MSThe spin quantum number, s, determines the magnitude of the spin angular momentum of an electron and has a value of .For a 1 electron species, msis the magnetic spin angular momentum and has a value of + or - . Sis the total spin quantum number p2)1(momentumangular Spin hSS for a multi-electron systemsSm MFor a system with nelectrons, each having s = , possible values of S(always positive) fall into two series depending on the total number of electrons: S= 1/2, 3/2, 5/2.

7 For an odd number of electrons. S= 0, 1, 2, .. for an even number of each value of S, there are (2S+ 1) values of MS:MS: S, (S-1), ..-(S-1), -S18{Microstates and term symbolsMicrostates the electronic states that are possible for a given electronic configuration. no two electrons may have the same set of quantum numbers (Pauli exclusion principle) only uniquemicrostates may be includedns2configurationCannot physically distinguish between the electrons, so must use sets of quantum numbers to decide if the microstates (rows in the table) are the same or microstate: l = 0, ml= 0, ms= +1/2; l = 0, ml= 0, ms= -1/2 Second microstate: l = 0, ml= 0, ms= -1/2; l = 0, ml= 0, ms= +1/2LS)12( Multiplicity of the termL = 0 S termL = 1 P termL = 2 D termL = 3 F termL = 4 G termTerm SymbolTable of microstates for an ns2configuration; an electron with ms= 1/2is denoted as , and an electron with ms= 1/2 is denoted as.}

8 The two microstates are identical and so one row can be discounted Terms for which (2S+1) = 1,2,3,4,.. are called singlet, doublet, triplet, quartet ns1 n s1configurationTable of microstates for an ns1n's1configuration. An electron with ms= 1/2 is denoted as , and an electron with ms= 1/2 as . Each row in the table corresponds to a different electrons in multi-electron systems: J and MJ p2)1(momentumangular TotalhJJ Total angular momentum quantum number Jtakes values: (L+ S), (L+ S-1) .. |L-S|and these values can be 0, 1, 2 .. or 1/2, 3/2, 5/2, ..Case 1: (2S+ 1) possible values of Jfor S< LCase 2: (2L + 1) possible values of Jfor L< value of MJdenotes the component of the total angular momentum along the values of MJ: J, J- 1, .., -(J- 1), method of obtaining Jfrom Land Sis based on LS(or Russell Saunders) coupling, aka spin-orbit coupling.{JSL)12( Multiplicity of the termL = 0 S termL = 1 P termL = 2 D termL = 3 F termL = 4 G termFull Term SymbolJ valueRules for Constructing a table of microstates1.}

9 Write down the electron configuration ( d2)2. Ignore closed shell electron configurations ( ns2, np6, nd10) as these will always give a Determine the number of microstates: for xelectrons in a sub-level of (2l+1) orbitals, this is given by:4. Tabulate microstates by mland ms, and sum to give MLand MSon each row. Check that the number of microstates in the table is the same as that expected from rule Collect the microstates into groups based on values of ML.}!)12(2{!)}!12(2{xlxl 20ml= 0ML= mlMS= mS 0+1/2}L = 0, S = 1/2 0-1/2 Microstates for Hydrogen, Z= !1!*1!2}!)12(2{!)}!12(2{smicrostate ofNumber xlxl2S1/2ml= 0, ml= 0ML= mlMS= mS 00}L = 0, S = 0 Microstates for Helium, Z= for Lithium, Z= for Beryllium, Z= for Boron, Z= the 2p1configuration contributes, but there are 3 distinct p !5!1!6}!)12(2{!)}!12(2{smicrostate ofNumber xlxlml= +1 ml= 0 ml= -1ML= mlMS= mS +1+1/2}L = 1, S = 1/2 0+1/2 -1+1/2 -1-1/2}L = 1, S = 1/2 0-1/2 +1-1/22P3/2or 2P1/2 Hund s RulesProviding that Russell-Saunders coupling holds,For the relative energies of terms for a given electronic configuration:1.

10 The term with the highest spin multiplicity has the lowest If two or more term have the same multiplicity ( 3 Fand 3P), the term with the highest value of L has the lowest energy( 3 Fis lower than 3P)3. For terms having the same multiplicity and the same values of L ( 3P0and 3P1), the level with the lowest value of Jis the lowest in energyif the sub-level is less than half-filled( p2), and the level with the highest value of Jis more stableif the sub-level is more stable if the sub-level is more than half filled( p4). If the level is half-filled with maximum spin multiplicity ( p3with S = 3/2), L must be zero, and J = for Carbon, Z= !4!2!6}!)12(2{!)}!12(2{smicrostate ofNumber xlxl2s22p2 Microstates for d2 (high spin)45!8!2!10}!)12(2{!)}!12(2{smicrosta te ofNumber xlxlTerm symbols: 23 Microstates for d2 (high spin), ordering of terms using Hund s Rules:Complexes and color A substance appears black if it absorbs all the visible lightthat strikes it, whereas if a substance absorbs no visible light it is whiteor colorless.