Coordination Chemistry II: Jahn-Teller, Square Planar Complexes, Orbital Overlap Method, and Electron Counting
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1 Coordination Chemistry II: Jahn-Teller, Square Planar Complexes, Orbital Overlap Method, and Electron Counting Chapter 10 and Section 13.3 Monday, November 30, 2015
2 Jahn-Teller Distortions Jahn-Teller Theorem: electron configurations with unequal occupancy of denerate orbitals are not stable. A complex with such a configuration will undergo a Jahn-Teller distortion to lower its energy. d 4 HS stabilization is driving force for distortion no net change in energy tetragonal elongation
3 Jahn-Teller Distortions Jahn-Teller Theorem: electron configurations with unequal occupancy of denerate orbitals are not stable. Various types of distortions are possible (tetragonal, trigonal, etc.). d 4 HS stabilization is driving force for distortion. no net change in energy tetragonal compression
4 Jahn-Teller Distortions Jahn-Teller Theorem: electron configurations with unequal occupancy of denerate orbitals are not stable. Only some complexes can lower their energy by distorting: d 5 HS no net change in energy no net change in energy tetragonal elongation No stabilization! No J-T distortion
5 Occurrence of Jahn-Teller Effects Partially occupied orbitals (M L σ*) lead to more pronounced distortions than partially-occupied orbitals (non-bonding). Strong Jahn-Teller Effect hs d 4 ls d 7 d 9 Weak Jahn-Teller Effect d 1 d 2 ls d 4 ls d 5 hs d 6 hs d 7
6 Square Planar Complexes Consider a CFT diagram of a tetragonal elongation taken to its extreme: dx2-y2 b1g dz2 dx2-y2 dxy dxz dyz dx2-y2 b1g dz2 a1g b2g dxy dxz dyz 1,sp Δ> Π b2g dxy a1g dz2 dxz dyz Octahedral tetragonal elongation removal of z ligands Square Planar
7 CFT of Square Planar Complexes Occurs mostly for d 8 i.e., Pd 2+, Pt 2+, Ir +, Au 3+ (majority low spin) Strong field ligands d x2 y2 d z2 d x2 y2 d xy d yz d xz d xy d z2 d z2 d x2 y2 d xy d yz d xz d yz d xz
8 Square Planar Complexes σ & π LFT diagram Be sure you know how to derive this by considering σ, π, and π separately
9 Angular Overlap Method The AOM provides a way to estimate the impact of metal-ligand interactions on the energy of the d orbitals (only used on d orbitals!). e σ is a native number because the in-phase or bonding interaction is favorable +e σ e σ Remember for an octahedral complex in the σ-only case only the dz2 and dx2 y2 orbitals interact with ligands eσ ¼eσ ¾eσ ¾eσ ¼eσ ¼eσ total energy 3eσ eσ ¼eσ total energy 3eσ ¾eσ ¾eσ
10 σ ML6 Octahedral MO Diagram 2t1u (n+1)p x y z T1u 2a1g (n+1)s s 2 A1g 3eσ= o nd z 2 x 2 y 2 xy xz yz Eg T2g A1g Eg T1u 1a1g 1t1u 1
11 Using the AOM The usefulness of the AOM is that it gives a good approximation of the energies of the metal d orbitals in different coordination geometries. the metal d orbitals are the frontier orbitals in most coordination complexes the AOM can be used to predict changes to the metal d orbitals if the coordination geometry is changed.
12 Using the AOM The usefulness of the AOM is that it gives a good approximation of the energies of the metal d orbitals in different coordination geometries. the metal d orbitals are the frontier orbitals in most coordination complexes the AOM can be used to predict changes to the metal d orbitals if the coordination geometry is changed. eσ 2eσ 3eσ 2eσ because dz2 drops so low in energy, squareplanar complexes are usually low-spin d 8 eσ
13 18 Electron Rule (Section 13.3) The 18 electron rule is a loose formalism for describing stable electron configurations for some transition metal coordination complexes. 18 electrons is the maximum number of electrons that can be accommodated by the metal nd, (n+1)s, and (n+1)p valence orbitals. really the 18 electron rule is an extension of the octet rule to include d orbitals the octet rule and the 18 electron rule are alternately know as the Effective Atomic Number (EAN) rule.
14 σ-only ML6 Octahedral MO Diagram 2t1u (n+1)p x y z 2a1g anti-bonding M L σ* T1u (n+1)s s A1g 2 For an octahedral complex, placing 6 electrons in the metal orbitals will give an 18 electron complex. nd z 2 x 2 y 2 xy xz yz M non-bonding Eg T2g A1g Eg T1u 1t1u 1a1g 1 bonding M L σ
15 18 Electron Rule The 18 electron rule is a loose formalism for describing stable electron configurations for some transition metal coordination complexes. 18 electrons is the maximum number of electrons that can be accommodated by the metal nd, (n+1)s, and (n+1)p valence orbitals. really the 18 electron rule is an extension of the octet rule to include d orbitals the octet rule and the 18 electron rule are alternately know as the Effective Atomic Number (EAN) rule. There are two methods for determining the total valence electron count for a transition metal complex Donor-Pair (ionic) counting method every ligand coordinated to the metal is considered to be a Lewis Base (i.e., a two electron donor) :NH3, :PR3, etc, are neutral Lewis Bases :Cl, :CH3, etc, are anionic Lewis Bases
16 Donor-Pair Method - Example 1 1. Remove all ligands as Lewis bases (closed octet on donor atom) tetramethylbis(trimethylphosphane)manganese 2 :PMe3 4 :CH3 2. Determine the charge left on the metal after removing the Lewis Base ligands. IV in order to balance charge, the manganese must be 4+, this is the metal oxidation state 3. Using the metal oxidation state, determine the number of metal d electrons #d electrons = #valence electrons in neutral metal metal oxidation state #d electrons Add the number of metal d electrons to the number of electrons donated by the ligands to get the total valence electron count. 2 :PMe3 4 :CH3 4 e 8 e So we d say that MnMe4(PMe3)2 is a d 3 Mn IV 3 e Mn IV 15-electron complex 15 e
17 Donor Pair Method - Example 2 pentaamminechlorocobalt (2+) 1. Remove all ligands as Lewis bases (closed octet on donor atom) 5 :NH3 :Cl 2. Determine the charge left on the metal after removing the Lewis Base ligands. 3. Using the metal oxidation state, determine the number of metal d electrons #d electrons = #valence electrons in neutral metal metal oxidation state #d electrons in this case the charge from removing the Cl must be added to the overall charge on the complex, giving us Co III 4. Add the number of metal d electrons to the number of electrons donated by the ligands to get the total valence electron count. 5 :NH3 10 e 1 :Cl Co III Co III 2 e 6 e 18 e So [Co(NH3)5Cl] 2+ is a d 6 Co III 18-electron complex
18 18 Electron Rule The 18 electron rule is a loose formalism for describing stable electron configurations for some transition metal coordination complexes. 18 electrons is the maximum number of electrons that can be accommodated by the metal nd, (n+1)s, and (n+1)p valence orbitals. really the 18 electron rule is an extension of the octet rule to include d orbitals the octet rule and the 18 electron rule are alternately know as the Effective Atomic Number (EAN) rule. There are two methods for determining the total valence electron count for a transition metal complex Donor-Pair (ionic) counting method every ligand coordinated to the metal is considered to be a Lewis Base (i.e., a two electron donor) :NH3, :PR3, etc, are neutral Lewis Bases :Cl, :CH3, etc, are anionic Lewis Bases Neutral Ligand counting method every ligand coordinated to the metal is considered to be a neutral species :NH3, :PR3, etc, are neutral two-electron donors to the metal Cl, CH3, etc, are neutral one-electron donors to the metal
19 Neutral Ligand Method - Example 1 1. Remove all ligands as neutral fragments, which leaves a neutral metal tetramethylbis(trimethylphosphane)manganese 2 :PMe3 4 CH3 Mn 0 2. Add up the electrons donated by the neutral ligands and on the neutral metal to get the total valence electron count 2 :PMe3 4 CH3 Mn 0 3. We still need to determine the metal oxidation state. 4 e 4 e 7 e 15 e Notice we again determine that MnMe4(PMe3)2 is a 15 electron complex metal OS = #one-electron donor ligands + charge on the complex metal OS Mn IV 4. Now, using the metal oxidation state, determine the number of metal d electrons #d electrons = #valence electrons in neutral metal metal oxidation state #d electrons 7 4 3
20 Neutral Ligand Method - Example 2 pentaamminechlorocobalt (2+) 1. Remove all ligands as neutral fragments, which leaves a neutral metal 5 :NH3 Cl Co 0 2. Add up the electrons donated by the neutral ligands and on the neutral metal to get the total valence electron count 5 :NH3 10 e 3. Determine the metal oxidation state. 1 Cl Co 0 1 e 9 e 20 e the charge on the +2 charge 2 e complex, which is e metal OS = #one-electron donor ligands + charge on the complex metal OS Co III 4. Using the metal oxidation state, determine the number of metal d electrons #d electrons = #valence electrons in neutral metal metal oxidation state #d electrons 9 3 6
21 18 Electron Rule There are two methods for determining the total valence electron count for a transition metal complex Donor-Pair (ionic) counting method every ligand coordinated to the metal is considered to be a Lewis Base (i.e., a two electron donor) :NH3, :PR3, etc, are neutral Lewis Bases :Cl, :CH3, etc, are anionic Lewis Bases Emphasizes metal oxidation state and d electron count Useful for all coordination complexes Neutral Ligand counting method every ligand coordinated to the metal is considered to be a neutral species :NH3, :PR3, etc, are neutral two-electron donors to the metal Cl, CH3, etc, are neutral one-electron donors to the metal Emphasizes EAN Useful for organometallic and other electron-rich complexes
22 Examples to try... hexacarbonylchromium d 6, Cr 0 18 electron complex hexamethylzirconate (2 ) d 0, Zr electron complex dichlorobis(pyridine)iron d 6, Fe electron complex triamminechloroplatinum (1+) d 8, Pt electron complex pentacyanocobaltate (3 ) d 7, Co electron complex Remember, you should get the same oxidation state, d-electron count, and total valence electron count rardless of which counting method you use!
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