CHM 3609 - Inorganic Chemistry

Chapter 6: Coordination Chemistry

Mark D. Jackson

jacksonm@fau.edu

Main Concepts: Examine the structure and reactions of coordination compounds - ions or ligands attached to a central metal atom. One or more ligands attach to a central atom or ion to forma stable complex... range of geometry and bond strength. MLxLyLzLx .. Review examples of compounds or complexes... Try to explain the observed structure and bonding... both are important due to isomerization. Guiding principles: VSEPR + orbital considerations + distortions Examine the electronic configurations of transition metal atoms or ions: * d0 or d10 - closed d-subshell - functions as a point-charge or bonding center * role of s-subshell that is often depleted to fill the d-subshell. * are there any lone pairs? * Examine geometry of d-orbitals that may remain open and participate in bonding. * in some cases the VSEPR system breaks down. MX2 - linear geometry - AX2 structure type. [Cl-Au-Cl]- [H3N-Ag-NH3]+ Au(I) MX3 - trigonal planar - AX3 [HgI3]Hg (II) - pyramidal- AX3E - tertrahedral - AX4 [Cu(CN)3]2Cu(I) d10, empty s-subshell [SnCl3]Sn(II) 5s2 4d10 lone pair Ag(I) - d10, empty s-subshell

need lone pair

MX4

non-transition metals... point charge VSEPR argument: Li(H2O)4+ Al(III) Transition metals symmetric - d10 d5 or d0, empty s-subshell [CoBr4]2- [Ni(CO)4] Co(II), Re(III), Ni need lone pairs or appropriate d-orbital d x2-y2 d8 Ni(II), Pd(II), Pt(II), Au(III); some d9 Cu(II) - 1 electron in this orbital similar energy Ni(II) [Ni(CN)5]3-

- square planar AX4E2 - trigonal bipyramid AX5 - square pyramid AX4E

MX5 MX6 -

octahedral - most common arrangement; fits with orbital interactions and stable charge arrangements. Distortions are common for asymmetric compounds; steric effects. - tetragonal (elongation), rhombic (angular), trigonal (3-3 twist)

> MX6 -

unusual compounds; it is hard to stabilize a group of anions around a central metal atom or cation. The steric effects and ionic repulsion will force the ligands away from one another and the metal atom.

Examples of Ligands Simple, monodendate - the ion(s) and metal attach at one point. Monatomic ions: halides, oxides; consider the effect of ion size and water hydration effects Hydroxide; forms a basic solution Small molecules - water, ammonia; note - polar, lone-pairs

Polydendate,

chelating ligands - clamp onto the metal using more than 1 bond or interaction; dendate - teeth Must consider bonding (enthalpy) and mixing effects (entropy). Common theme: oxygen and nitrogen lone pairs.

en - ethylenediamine H2N-CH2-CH2-NH2 - nitrogen lone pairs are the reactive site. oxygen lone pairs Glyme - H2C-O-CH2-CH2-O-CH2 terpyridine, bipyridine - N lone pairs. Planar aromatic systems... 2 and 3 ring. Porphyrin - tetradendate 4 planar rings Metal-ring componds: Carbonate and similar anions can form a 4-member ring - >M
X L >M< X cis L L trans X | L >M< L | L X trans X >M< X L

Structure variation: a number of types of isomerization: use a model kit... Geometrical: ML4 => ML2X2 (cis or trans) - for square planar or tetrahedral.... ML5X - X may occupy axial or equatorial position. ML4X2 (cis or trans) ML3X3 (facial or meridional). Optical: chiral - the spatial arrangement of the ligands is altered.... same bonding configuration Form mirror images... rotate plane polarized light M(L-L)3 or MX2 (L-L)2 lamda - laevorotary - left delta - dextrorotary - right Example: Tris-chelate - M(en)3 fan-blade or spiral imagery Linkage: A ligand may exhibit different bonding connectivity. NO2 - can bond to O or N (also resonance effect) Ionization: the complex can dissociate in different ways. [Co(en)3(NO2)Cl] SCN SCN can exchange with en or NO2 Ligands can occupy 1st or 2nd coordination sphere, intermingles with solvent molecules. Coordination: 2 coordinated metals can exchange ligands [(M1L6 )(M2X6 )] == > exchange of L and X Nomenclature and formulas: IUPAC system. Goal: provide clear description of the bonding in the compound. Clearly show composition of metal complex ions; Prefixes, Bracketed complex ions Formation of Coordination Compounds from metal atom/ion and ligands Review basic concepts of equilibrium vs. complete reactions, shifting of LeChatlier etc. Kinetics vs. thermodynamics: energetic stability vs. mechanism; review SN1, SN2 as examples.

X | L >M< L | L L cis X

X | L >M< X | L L facial Meridional X

X | L >M< X | L X L

/ L L \ | L L | L >M< ) ( >M< L | L L | L \ L L / mirror images L

Concepts: Coordination equilibrium - M Lx formation may involve a number of steps; for each step, specify the Keq: K1, K2, K3, etc... - the overall stability constant M + n L <=> M Ln K1,x K2, x K3 .... x Kn = Example: [Cd(NH3 )4]2+ K1 = 102.65 Cd 2+ + NH3 <=> [CdNH3 ]2+ 2+ 2+ [CdNH3 ] + NH3 <=> [Cd(NH3 )2] K2 = 102.10 2+ 2+ [Cd(NH3 )2] + NH3 <=> [Cd(NH3 )3] K3 = 101.44 2+ 2+ [Cd(NH3 )3] + NH3 <=> [Cd(NH3 )4] K4 = 100.93 2+ 2+ Overall: Cd + 4 NH3 <=> [Cd(NH3 )4] = K1,x K2, x K3 x K4 = 10(2.65 + 2.10 + 1.44 + 0.93) = 107.12 Hess Law: add reactions, add thermodynamic values, multiply the K values from each step.

Equilibrium: entropy and enthalpy contribute to free energy, and therefore the equilibrium constant., Mixing: thermodynamic factors are enthalpy & entropy - ideal mixing driven by entropy.

Exothermic reactions (combustion): enthalpy dominates the free energy of the process. Chelate effect: certain coordination compounds have a larger value than expected. Example: Compare the for [Ni(NH3)6]2+ vs. [Ni(en)3]2+ hexa amine: 6 =109 Tris en: 3 = 1018 (Favored product) =109.7 Why? Examine: [Ni(NH3)6]2+ + 3 en <=> 6 NH3 + [Ni(en)3]2+ Greater number of amine molecules enhances the disorder of the product, even though the metal complex is more ordered. (larger S, more negative G) For this process, H is small, only -12 KJ; G is -67 KJ, leaving -55 kJ for -TS Compare kinetic and thermodynamic control; speed vs. stability; must examine the reaction mechanism, i.e. the activation energy of the transition state, and the H of the overall reaction. Reactions with comparable Ea are thermodynamically controlled (H varies) Reactions with comparable H are kinetically controlled (Ea varies). Speed of exchange: labile (fast) and inert (slow)... a kinetic effect. Thermodynamics: stable; degree of stability based on bond energies. Type of Ligand exchange reactions: Y + ML5X ==> YML5 + X SN1-type: Dissociative, 2 steps: ML5X ==> ML5 + X Y + ML5 ==> YML5 SN2-type: Associative or concerted reaction; 1 step: Y + ML5X ==> {Y ML5 X} ==> YML5 + X Variables and factors: Solvent interactions impact polar or charged species, especially ion-pair formation; Relative strengths of M-Y and M-Y; lability of X and Y. Examples: 1. Water Exchange process (octahedral): Between inner (molecules nearer the cation or M, bonded) and outer sphere water (molecules around the M(H2O)x complex) Larger charge, larger interactions, slower exchange; Larger ionic radii, more diffuse charge, water is more loosely held in place. Transition metal d-orbital effects... variable. 2. Anation: addition of an anion to octahedral complex. [M(H2O)6]n+ + X- ==> [M(H2O)5X](n-1)+ + H2O Options: associative or dissociative; later is observed. Observations: for a given metal, rate is independent of X; rate is comparable to water exchange rate (rate limiting step). Step 1: Form outer sphere complex (fast), Step 2: Inner sphere water moves to the outer sphere (slow), Step 3: X joins the inner coordination (fast). 3. Aquation: Water displaces ligand on octahedral. Usually require acid (dissociative) or base (associative) hydrolysis steps. Rate = acid hydrolysis + base hydrolysis = ka [ML5X]+n [H2O] + kb [ML5X]+n [OH-] Must examine both reaction paths; may vary with ligand and metal, and depend on water exchange processes. 4. Reactions of square-planar complexes: less steric effects, but must also examine two paths and role of water in each step Key to these application is the solvent structure, especially water. We forget that reactive molecules must move into place and work around non-reactive solvent molecules. Types of Problems: Section A: 1,4,7,8, 11,13,14 Section B: 2,3,5,6

i. predict geometries of complexes. ii. use orbital models to explain geometries. iii. how do ligands bind to metals. v. discuss possible isomers for a given compound. vi. describe equilibrium for metal ligand reactions. vii. compare thermodynamic and kinetic reaction factors. viii. summarize major types of ligand substitution mechanisms. ix. inner sphere/outer sphere solvent effects. x. variation of mechanisms: solvent, ion-pair. xi. analysis of rates in terms of metal charge and size.