FACULTY OF SCIENCE AND FACULTY OF ETERNAL STUDIES BACHELOR OF EDUCATION (BED SCI) SCH 304: INORGANIC CHEMISTRY 4 CO-ORDINATION CHEMISTRY.

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1 FACULTY OF SCIENCE AND FACULTY OF ETERNAL STUDIES BACHELOR OF EDUCATION (BED SCI) SCH 304: INORGANIC CHEMISTRY 4 CO-ORDINATION CHEMISTRY Written by Dr Lydia W. Njenga Department of chemistry Reviewed by Prof. Shem O Wandiga Department of chemistry Edited & Coordinated by: J. O. Odumbe Director CO &DL - i -

2 SCH 304 INORGANIC CHEMISTRY 4 (COORDINATION CHEMISTRY) COURSE OUTLINE PAGE INTRODUCTION vii REFERENCES viii PERIODIC TABLE ix LECTURE 1 INTRODUCTION OF TRANSITION ELEMENTS 1:1 Introduction 1 1:2 Electronic configurations. 2 1:3 Properties of transition elements 3 1:4 Ground state term symbols- the Russel Saunders coupling scheme 5 LECTURE 2 COORDINATION COMPOUNDS 2:1 Introduction 14 2:2 Introductions to coordination compounds 15 2:3 Types of ligands 16 2:4 Oxidation Number 18 2:5 Nomenclature 20 2:6 Evidence of coordination 21 - ii -

3 2:7 Effective Atomic Number (EAN) or 18-electron rule 23 LECTURE 3 Stereochemistry 3:1 Introduction 25 3:2 Stereoisomerism 26 3:3 Geometrical isomer 26 3:4 Linkage isomers 28 3:5 Ionization isomers 29 3:6 Bridged isomers 31 3:7 Optical isomers 31 LECTURE 4 Valence Bond Theory (VBT) 4:1 Introduction 34 4:2 Assumption 34 4:3 Hybridization 35 4:4 Tetrahedral Complexes 38 4:5 Square planar 39 4:6 Failure of Valence Bond Theory 39 LECTURE 5 Crystal field Theory (CFT). 5:1 Introduction 41 5:2 Crystal field splitting for Octahedral (O h ), 41 5:3 Ground state electronic configurations d 1 d :4 Factors affecting magnititude of :5 Splitting of d orbital of lower symmetry 57 5:6 Crystal field stabilization energies 60 - iii -

4 LECTURE 6 EVIDENCE FOR THE SPLITTING OF THE D ORBITALS IN CFT OR LFT 6:1 Introduction 65 6:2 Structural Ionic radii 66 6:3 Thermodynamic factors 67 LECTURE 7 ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES 7:1 Introduction 71 7:2 The splitting of the states 72 7:3 Origin of Color 75 7:4 Selection rules 78 7:5 Electronic spectra of some complexes 80 7:6 Microstates 82 7:7 Orgel and Tanabe Sugano diagrams 85 LECTURE 8 ADJUSTED CRYSTAL FIELD THEORY (ACFT) OR LIGAND FIELD THEORY (LFT) 8:1 Introduction 91 8:2 Assumption 91 8:3 Spin orbit coupling 93 8:4 Interelectronic repulsion parameters 93 8:5 Nephelauxetic effect 97 - iv -

5 LECTURE 9 MOLECULAR ORBITAL THEORY (MOT) 9:1 Introduction 99 9:2 Formation of molecular orbitals in octahedral 100 9:3 Complexes without orbitals ( metal ligand δ interactions) :4 Complexes with orbitals. (metal ligand bonding) 109 9:5 Comparison of VBT and MOT 114 9:6 Comparison of CFT and MOT 114 LECTURE 10 MAGNETISM 10:1 Introduction :2 Diamagnetism :3 Paramagnetism 118 LECTURE 11 JAHN TELLER EFFECT 11:1 Introduction :2 Theorem :3 Jahn Teller Distortion effect :4 Stabilization energy :5 Effect of Jahn Teller on the spectra v -

6 LECTURE 12 CHARGE SPECTRA 12:1 Introduction :2 Definition :3 Intra - Ligands Transition :4 Ligand Metal Transition :5 Metal Ligand Transition :6 Metal Metal Transition 137 ANSWERS TO ACTIVITY vi -

7 INTRODUCTION I would like to take this opportunity to welcome you to the third year inorganic chemistry 4 on the chemistry of coordination compounds. For this unit Knowledge of inorganic chemistry 1 and 2 will be required. In inorganic chemistry 1 you were introduced to the structure of the atom, electronic configuration, shapes of the molecules, molecular orbital energy diagrams and the periodic table. In inorganic chemistry 2 you covered the chemistry of the s and p block elements of the periodic table. During the study of this unit, we will try to broaden your knowledge on the chemistry of the transition elements (d and f block elements) by looking at the chemistry of coordination compounds. The study of coordination will cover the nomenclature, stereochemistry, working out the state term symbols and bonding. Bonding will be discussed under valence bond theory, Crystal field theory, adjusted crystal field theory and molecular field theory. To study the properties of the coordination complexes, electronic spectra (d d transition and charge transfer) will be used to discuss the occurrence of different colors in complexes while magnetic moments will be used to explain the magnetism of the compounds. The unit has been divided into 12 lectures which will be covered within one semester. Each lecture starts with a short introduction, objectives and followed by the discussion of the lecture. Furthermore each lecture has worked out examples which are easy to follow. At the end of each topic practice activities are given which you are expected to do. Answers of the activities are given at the end of lecture 12. You are expected to do the excise first without looking at the answers and then mark for yourself. The course will constitute 70% of the final examination and 30% continuous assessment tests. The materials presented in this unit are very comprehensive. However you are advised to make reference to the following text books below. During your residential training, the aspects of the course which you find will be explained. - vii -

8 REFERENCE 1. F.A Cotton and G. Wilkinson (1969) Advanced Inorganic Chemistry, John weily and Sons, New York - viii -

9 2. S.F.A Kettle Co-ordination compounds Thomas Nelson and sons Ltd: William W. Porterfield Inorganic chemistry. A unified approach Addison-Wesley Publishing company: Raymond Chang Chemistry 4 th edition, McGraw-Hill Company 5. William L. Jolly Modern inorganic chemistry McGraw-Hill Company 6. Satya Prakash, G. D. Tuli, S. K. Basu and R. D. Madan, 2000, Advanced Inorganic Chemistry S. Chard & company, Ram Nagar, New Delhi. 7 Any other Inorganic chemistry book - ix -

10 Main Group Elements I II III IV 1 H 1s 1 3 Li 2s 1 11 Na 3s 1 19 K 4s 1 37 Rb 5s 1 55 Cs 6s 1 87 Fr 7s 1 4 Be 2s 2 12 M g 3s 2 20 Ca 4s 2 38 Sr 5s 2 56 Ba 6s 2 88 Ra 7s 2 Transition Elements III IV V VI VII VIII I II 21 Sc 3d 1 4s 2 39 Y 4d 1 4s 2 57 La 5d 1 6s 2 89 Ac 6d 2 5f 14 7s 2 22 Ti 3d14s 2 40 Zr 3d 2 4s 2 72 Hf 104 Rf 6d 2 5f 14 7s 2 23 V 3d 3 4s 2 24 Cr 3d 5 4s 1 25 Mn 3d 5 4s 2 41 Nb 4d 3 5s 2 42 Mo 4d 5 5s 1 43 Tc 4d 5 5s 2 73 Ta 74 W 75 Re 105 Ha d 2 5f 14 7s 2 6d 2 5f 14 7s 2 6d 2 5f 14 7s 2 26 Fe 3d 6 4s 2 44 Ru 4d 6 5s 2 76 Os 27 Co 3d 7 4s 2 45 Rh 4d 7 5s 2 77 Ir 28 Ni 3d 8 4s 2 46 Pd 4d 8 5s 2 78 Pt 5d 9 4f 14 6s 1 29 Cu 3d 10 4s 1 47 Ag 4d 10 5s 1 79 Au 5d 10 4f 14 6s 1 30 Zn 3d 10 4s 2 48 Cd 4d 10 5s 2 80 Hg 5 B 2p 1 13 Al 3p 1 31 Ga 4p 1 49 In 5p 1 81 Tl 6p 1 6 C 2p 2 14 S 3 p 32 G 4p 2 50 Sn 5p 2 82 Pb 6p 2 Lanthanide Elements Actinide Elements 58 Ce 5d 0 4f2 1 6s 2 90 Th 6d 2 5f o 7s 2 59 Pr 5d 0 4f 34 6s 2 91 Pa 6d 1 5f 2 7s 2 60 Nd 5d 0 4f 4 6s 2 92 U 6d 1 5f 3 7s 2 61 Pm 5d 0 4f 5 6s 2 93 Np 6d 1 5f 4 7s Sm 5d 0 4f 6 6s 2 94 Pu 6d 0 5f 6 7s 2 63 Eu 5d 0 4f 7 6s 2 95 Am 6d 0 5f 7 7s 2 64 Gd 5d 0 4f 8 6s 2 96 Cm 6d 1 5f 7 7s 2 65 Tb 5d 0 4f 9 6s 2 97 Bk 6d 0 5f 9 7s 2 66 Dy 5d 0 4f 10 6s 2 98 Cf 6d 0 5f 10 7s 2 67 Ho 5d 2 4f 11 6s 2 99 Es 6d 0 5f 11 7s d d

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