Isomerism - Stereoisomers
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1 Isomerism - Stereoisomers 6 CN ; Octahedron, Triethylentetraamine H 2 N H N N H NH 2 No coplanar rings Two coplanar rings Three coplanar rings
2 Isomerism - Stereoisomers Number of possible Isomers
3 Isomerism - Stereoisomers Number of possible Isomers Ma 3 bcd a facial d a c a b no mirror plane meridional a a a a a b d c a d a d a b a b a c c a b d a c
4 Isomerism - Stereoisomers Number of possible Isomers
5 Isomerism Stereoisomers: Combination of Chelate Rings (, ) Handedness of chelate Rings Lambda Delta
6 Isomerism Stereoisomers: Combination of Chelate Rings (, ) [Co(en) 3 ] 3+
7 Isomerism Stereoisomers: Combination of Chelate Rings (, ) Procedure for Determining Handedness
8 Isomerism Stereoisomers: Combination of Chelate Rings (, ) CoEDTA - Not coplanar, not connected at the same atom X X R1: R2, R3, R4, R5 X X X R2: R1, R3, R4, R5,, or
9 Isomerism Stereoisomers: Lignad Ring Conformation 6 CN ; Octahedron, Triethylentetraamine H 2 N H N N H NH 2 S S S S R R R R
10 Isomerism Stereoisomers: Lignad Ring Conformation Chelate Ring Conformation (λ, δ)
11 Isomerism Stereoisomers: Lignad Ring Conformation 6 CN ; Octahedron, Triethylentetraamine Chelate Ring Conformation (λ, δ)
12 Isomerism Constitutional Isomers: Hydrate Isomers Hydrate Isomers: having water as either a ligand or an added part of the crystal structure
13 Isomerism Constitutional Isomers: Ionization Isomerism Ionization Isomers: Exchange of ions between inside and outside coordination sphere
14 Isomerism Constitutional Isomers: Coordination Isomerism Coordination Isomers: require at least two metal
15 Isomerism Constitutional Isomers: Linkage (ambidentate) Isomerism Linkage Isomers: Compounds containing ambidentate ligand thiocyanate thiocyano isothiocyano nitrite nitro nitrito
16 Isomerism Separation and Identification of Isomers Separation Fractional Crystalization packing, solubility, size, charge Chiral Isomers Resolution chiral counterions Identification X-ray crystallography Optical rotatory dispersion (ORD) Circular dichroism (CD)
17 Coordination Numbers and Structures Structures vs Properties. Factors for Structures 1. Number of Bonds Bond formation is usually exothermic. So stability 2. VSEPR 3. Occupancy of d orbitals Square-planar vs Tetrahedral 4. Steric Effects 5. Crystal Packing Effects Crystalline Lattice vs Solution What is common thing? Which one is a dominant factor? CN Geometries Rare Linear Trigonal-plane Tetrahedron, Square-plane Trigonal bipyramid, Square pyramid Octahedron, Trigonal prosm Pentagonal bipyramid, Capped trigonal prism, Capped octahedron Known up to 16 CN
18 Coordination Numbers and Structures Oxidation States of Transition Metals
19 Coordination Numbers and Structures CN = 1,2, and 3 CN = 1, Rare
20 Coordination Numbers and Structures CN = 1,2, and 3 CN = 2, Rare, Linear (D h ) Mostly d 10 metals, Ag(I), Cu(I), Au(I), Hg(II) d 5, d 6, d 7 Examples of CN = 2 Large Ligands can induce a linear arrangement
21 Coordination Numbers and Structures CN = 1,2, and 3 CN = 3, Rare, Trigonal planar (D 3h ) Mostly d 10, PPh 3, N(SiMe 3 ) 2, Bulky enough, Steric effect vs Electroic structure
22 Coordination Numbers and Structures CN = 4 CN = 4, Tetrahedral (T d ) Squre-planar(D 4h ) Tetrahedral (T d ) ; very common,
23 Coordination Numbers and Structures CN = 4 CN = 4, Tetrahedral (T d ) Squre-planar(D 4h ) Squre-planar(D 4h ) ; mostly d 8 (Pd(II), Pt(II), Ni(II), Ag(III), Ir(I) Rh(I)) Tetrahedral vs Square-planar Counterion, Crystal Packing Cl Cl Cu Cl Cl 2Cs
24 Coordination Numbers and Structures CN = 4 CN = 4, Tetrahedral (T d ) Squre-planar(D 4h ) Squre-planar(D 4h ) ; mostly d 8 (Pd(II), Pt(II), Ni(II), Ag(III), Ir(I) Rh(I)) Tetrahedral vs Square-planar Counterion, Crystal Packing E is not big.
25 Coordination Numbers and Structures CN = 5 CN = 5, Trigonal bipyramid (D 3h ), Square pyramid (C 4v ) Fluxional behavior.
26 Coordination Numbers and Structures CN = 6 CN = 6, Octahedral (O h ) most common O h to D 4h
27 Coordination Numbers and Structures CN = 6 CN = 6, Octahedral (O h ) to Trigonal Prism (D 3h ) Usually with three bidentate ligands
28 Coordination Numbers and Structures CN = 7 CN = 7, Pentagonal bipyramid (O h ), Capped trigonal prism, Capped octahedron Capped trigonal prism Pentagonal bipyramid Capped octahedron Different counterion, steric requirment
29 Coordination Numbers and Structures CN = 8 CN = 8, Square antiprism, Dodecahedron Eight coordination is rare in the first row transition metals Square antiprism Why? Central ion must be large in order to accommodate eightcoordination Dodecahedron
30 Coordination Numbers and Structures CN 8 CN 8, known up to 16, not common
31 Multimetallic Compexes Without direct M-M bond With direct M-M bond
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