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Lecture Note 3

These are coordinate chemistry lecture notes

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Lecture Note 3

These are coordinate chemistry lecture notes

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Hasitha
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© © All Rights Reserved
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CHE 202 1.0 Chemistry of Coordination Compounds Lecture Notes Prepared by: Dr. Mahesh Karunarathne Department of Chemistry University of Sri Jayewardenepura 08/08/2020 Crystal Field Theory (CFT) yy * Assumption: the bonding between the metal ion and the ligands is purely ionic (electrostatic). = Metal ion and ligands are taken as positive and negative point charges, respectively. = d-Orbitals of the central metal ion lose their degeneracy due to the influence of the ligands electrostatic field around the metal ion. ve " t,, orbitals: d,, , d,., dy, e, orbitals: d,2, d,2y2 Crystal Field Theory (CFT) XQ = d-o1 | energy = The five d-orbitals in an isolated metal ion are degenerate. = Ina spherical electrostatic field the energy of the d-orbitals are raised but the orbital degeneracy is preserved. Orbital Ma, M, lav Mdaa energy Pll = —_—— a Bday 3d 3p rate Degenerate ‘The 3d atomic orbitals 3d atomic orbitals 3 atomic orbitals ae plit into two levels In a non-spherical field created by 4 or 6 ligands, the energies of t,, and e, orbital sets split (become non-degenerate). The Octahedral Crystal Field yy Ligands approach the metal ion along x, y, and z axes. e, orbitals with lobes pointed along the axes are repelled strongly by the ligand field than the t,, orbitals pointed between the axes. Thus, the d,2 and d,2_,2 atomic orbitals are destabilized (high energy) to a greater extent than the dy, d,,, and d,, atomic orbitals. However, the mean energy remains unchanged relative to the energy of the d orbitals in a spherically symmetrical environment The Octahedral Crystal Field XQ = The energies of the d orbitals in an octahedral crystal field. = A, = octahedral crystal field splitting energy " The overall stabilization of the t,, orbitals equals the overall Spherical Beheasl destabilization of the e, set. environment crystal field Thus, 4x- 6y=0 4x = 6y @ From @, @; x= %A, andy = %A, A,=xty The Octahedral Crystal Field yy A, is an experimental quantity. The octahedral crystal field splitting energy, A, = 10 Dq, Thus, x = 6 Dq, and y = 4 Dq, Spherical Octahedral The magnitude of A, is determined environment crystal field by the strength of the crystal field generated by the ligands as well as the identity and oxidation state of the metal ion. A, (weak field) < A, (strong field) Structure and chemistry of coordination compounds depend on the number and the distribution of d-electrons in the metal ion. Crystal Field Stabilization Energy (CFSE) XQ = For a given a” configuration, the CFSE is the difference in energy between the d electrons in an octahedral crystal field and the d electrons in a spherical crystal field For octahedral complexes with d!-d? configurations a” electrons Electronic configuration CFSE at igiel -4Dq, a tog ey" -8 Dg, d t? e,° -12 Dq, All are high-spin Crystal Field Stabilization Energy (CFSE) yy dé-d?° configurations could be high- or low-spin in octahedral complexes E.g. d* ion has two available arrangements: ty 2 e,! high-spin and t,,* e,” low-spin configurations. 9 Pairing energy (P) must be provided to overcome the Coulombic repulsion between the two electrons to pair. For high-spin: 4, < P whereas for low-spin: A, > P Crystal Field Stabilization Energy (CFSE) * High-spin octahedral complexes (where A, P) electrons | Electronic configuration CFSE a -16 Dg, a -20 Dg, a -24 Dg, v -18 Dg, a -12 Dg, @& -6 Dq, a? 0 Crystal Field Stabilization Energy (CFSE) XQ For octahedral d° complexes with n = 1-3 and 8-10 there is no ambiguity about the configuration, and the designations high-spin and low-spin are not used. Pag > Pag > Poa Because, 4d and Sd orbitals are less compact and electron-electron repulsions correspondingly weaker. Thus, complexes of 4d and 5d metals generally have low-spin electron configurations. E.g. [Ru(ox),]; is low-spin t,,° [Fe(ox)3]; is high-spin t,,3 e,? UV-Vis Spectrum of Coordination raisin E.g. Consider the d# complex, [Ti(H,0) .]** in its ground state, > Abworbance oo —1s000 20000 25.000 ™ Amox Corresponds to the electron transition from t,, > e, " Thus, AE = A, = hc/A = 243 kJ mol* Spectrochemical Series XQ Ligand-eld splitting parameters A, of ML, complexes ce 13700 7400 21 500 21900 26600 © Mn 7500 8500 10 100 30000 Fe 11000, 14300 (35.000) ee 10400 (32800) coe (20700) (22.900) (23200) (34800) Rr (20400) (27000) (34.000) (34600) (45 500) e Nee 7500 8500 10 800 11 500 Increasing 4, Weak field ligands Strong field ligands = F< Br <$? = F< Br Mle tetrahedral octahedral * Stability of low-spin octahedral complex (with strong field ligands) will be greater than that of a high-spin complex = Octahedral site stabilization energy (OSSE) Orbital A cy ee High-Spin Octahedral Vs Tetrahedral XQ napa - | | {| | k "Eg: d! CFSE (octa) = -4 Dg, [| \ CFSE (tetra) = -6 Dq, = -2.67 Dg, OSSE = -1.33 Dq, = CFSE has no bearing on the geometry of d®, high-spin d°, and a? ions = d? and d® ions strongly prefer 0 an octahedral geometry over O1234 567801 Number of electrons, a tetrahedral one The ligand-feld stabilization = d? and d® ions show the highest energy for d” complexes in octahedral (high-spin, circles) and tetrahedral (squares) tendency to form tetrahedral complexes. The LFSE is shown in terms of A,, geometry by applying the relationship A, = # A,, Square-Planar Complexes yy * Fact: d? configuration, coupled with a strong ligand field, favors the formation of square-planar complexes. + Loo" Loot 4 4" Leragl gob biting gel Lan, wk a aly =i eps uw |. uN uw L L cS L Octahedral complex Removal of axial Square ligands planar complex * Tetragonal distortion (z-out) Square-Planar Complexes XQ yzy2 yay: xz, dye Octahedral Tetragonally Square distorted planar Milo — Mh My, Energy Square-Planar Complexes yy Idee—ye "= The electronic stabilization energy of some square-planar d® complex with low-spin [Ae d2, d3z d2z dy configuration hy can more than compensate for La any unfavorable steric Hee interactions. HTH fee dye Octahedral Square planar * Eg. Rh(I), Ir(i), Pt(ll), Pd(Il), and Au(Ill) ions Experimental Facts to Support CFSE XQ = Lattice energies for MX, compounds s — Lattice energy/kJmol* s 8 ro) Oo 1 2 3 4 5 6 7 8 9 1 Number ofd electrons In each salt, the metal ion is high-spin, octahedral in the solid state Only Ca?*, Mn?*, and Zn‘, whose CFSE = 0, follow the trend line. Other ions get extra stability through CFSE Experimental Facts to Support CFSE yy Enthalpies of hydration of M2* ions adhd o t 2 3 4 § 6 7 & 9 W Number of electrons Water is a weak-field ligand and [M(H,0),]* ions of the first row transition metals are high-spin. Only Ca?*, Mn, and Zn*, whose CFSE = 0, follow the trend line. Straight line is obtained when the CFSE’s are subtracted from experimental data for d’ and d°-d? metal-hydrates. Experimental Facts to Support CFSE XQ ® lonic radii lonic radius (pm) Increasing atomic number —> Jahn-Teller Distortion yy * Fact: Octahedral complexes of d®, high-spin d and low-spin d? ions are often distorted. = Two metal-ligand bonds (axial) are different lengths from the remaining four (equatorial) * E.g. CuF, , [Cr(H,0),]?* , Pd{(ttl) = E.g. Crystal structure of CrF, forms a distorted octahedral structure with four bond lengths 1.98 A and two longer bonds having length 2.43 A Jahn-Teller Distortion XQ = Jahn-Teller theorem: 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. If the ground electronic configuration of a nonlinear complex is orbitally degenerate, and asymmetrically filled, then the complex distorts so as to remove the degeneracy and achieve a lower energy. * Asymmetrically filled e, orbitals Jahn-Teller Distortion yy = Extension along the z-axis and compression on the x- and y-axes, x-¥ lowers the energy of the d,2 orbital 2 and increases the energy of the d,2,2 orbital = high-spin d* and low-spin d’: (¢g) dja d)2_y2 a e 2 gh yam (Cg) des dts ye = Axial elongation is more common Octahedral —Tetragonal 4 - (weakens two bonds) than axial The effect of tetagonal distortions Fi (conmprestion aloes xand yaad compression (weakens four bonds) ‘extension along 2) on the energies ne Stdorbitals Tre eeton sccupaton _-*®-Sitmilar distortions in unequally iforadcomplex occupied t,, set are less pronounced Jahn-Teller Distortion XQ Visible region of the UV-vis spectrum (absorption) of [Ti(H,0)],>* has a shoulder d', octahedral complex Degenerate ground state. Excited state undergo Jahn-Teller distortion dy : ds q, ky . SE dye, dye Magnetic Measurements of Coordination yy Compounds Magnetic measurements are used to determine the number of unpaired spins in a complex and hence to identify its ground-state configuration Paramagnetism arises from unpaired electrons Diamagnetic compounds are repelled by a magnetic field Paramagnetic compounds are attracted by a magnetic field The magnitude of the paramagnetism of a complex is expressed in terms of the magnetic dipole moment (11). In a free atom or ion, both the orbital angular momentum and the spin angular momentum of electrons give rise to a magnetic moment. Spin-only Magnetic Moment XQ w= V4S(S+D+ L410) S= total spin angular momentum quantum number L = total orbital angular momentum quantum number The contribution to the magnetic moment by the orbital motion is insignificant for first row transition metals in complexes. * Thus, u, = (45(S+1). For one unpaired electron, $ = 1/2 = For n number of unpaired electrons, $ = n/2 Hence, u1, = n(n +2) is given in Bohr magneton, 1 BM = 9.274 x 1074 J T* Spin-only Magnetic Moment yy * Calculated spin-only magnetic moments (high-spin) ‘Metal ion a 5 Meq(spin-only) Observed values configuration Of peer a 0 0 0 a Ys 173 178 a 1 283 283.1 a Ya 3.87 3.23.9 a 2 4.90 48-49 a Yy 592 5.7-6.0 ae 2 4.90 5.0-5.6 a 4, 3.87 4352 a 1 2.83 29-39 da Ya 1.73 19-21 a® 0 0 0 Experimental 4g is slightly greater than y,, calculated. This is due to the orbital contribution. Spin-only Magnetic Moment XQ A measurement of the magnetic moment of a d-block complex can be used to distinguish between high-spin and low-spin complexes. E.g. K,[FeF,] is paramagnetic with a magnetic moment of 5.9 BM whereas K,[Fe(CN),] has = 2.3 BM. Fe? = 3d°,, octahedral geometry K,[FeF] * K[Fe(CN)g] 5 unpaired electrons = 1unpaired electrons Must be high spin = Must be low spin ott = Limitations Associated with CFT yy Neutral complexes like, Ni(CO), cannot be described. No point charges. No electrostatic attractions. Bonding must be more covalent than ionic. CFT does not take into account the overlap of ligand and metal atom orbitals. CFT does not provide explanation as to why particular ligands are placed where they are in the spectrochemical series.

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