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Unless otherwise stated, all images in this file have been reproduced from: Blackman, Bottle, Schmid, Mocerino and Wille, Chemistry , 2007 (John Wiley)      ISBN: 9 78047081 0866. CHEM1002 [Part 2]. A/Prof Adam Bridgeman (Series 1) Dr Feike Dijkstra (Series 2) Weeks 8 – 13

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  1. Unless otherwise stated, all images in this file have been reproduced from: Blackman, Bottle, Schmid, Mocerino and Wille,Chemistry, 2007 (John Wiley)     ISBN: 9 78047081 0866

  2. CHEM1002 [Part 2] A/Prof Adam Bridgeman (Series 1) Dr FeikeDijkstra (Series 2) Weeks 8 – 13 Office Hours: Monday 2-3, Friday 1-2 Room: 543a e-mail:adam.bridgeman@sydney.edu.au e-mail:feike.dijkstra@sydney.edu.au

  3. Summary of Last Lecture • Complexes II • For octahedral complexes with formulae [MX2Y4], cis and trans geometrical isomers are possible • For square planar complexes with formulae [MX2Y2], cis and trans geometrical isomers are possible • For octahedral complexes with bidentateligands, optical isomerism is also possible • Metal complex formation can greatly increase solubility

  4. Complexes III • Lecture 14 • Transition Metals • Electron Configuration • Oxidation States • Colours • Magnetism • Blackman Chapter 13, Sections 13.4 and 13.7 • Lecture 15 • Metals in Biological Processes • Essential Elements • Toxic Elements • Medicinal Uses • Blackman Chapter 13

  5. Transition (or d-block) Metals

  6. Subshells (from CHEM1001 lecture 14) • Each shell is divided into subshells called s, p, d, f…. • There is one extra subshell for each new shell • First shell: 1s • Second shell: 2s and 2p • Third shell: 3s, 3p and 3d • Fourth shell: 4s, 4p, 4d and 4f

  7. Filling Subshells (from CHEM1001 lecture 14) • 2 electrons can fit into a s subshell • 6 electrons can fit into a psubshell • 10 electrons can fit into a dsubshell • 14 electrons can fit into a fsubshell energy increases energy increases

  8. Electronic Configurations of Atoms • Each sub shell is made from “orbitals” which can each accommodate up to 2 electrons: • 2 electrons can fit into a s subshell in one orbital • 6 electrons can fit into a psubshell in threeorbitals • 10 electrons can fit into a dsubshell in fiveorbitals s p 3d

  9. Electronic Configurations of Cations • Main group metals like Na, K, Mg and Ca lose allof their valence electrons • Na: [Ne] 3s1 • Na+: [Ne] 3s0 or just [Ne] • Mg: [Ne] 3s2 • Mg2+: [Ne] 3s0 or just [Ne] • K: [Ar] 4s1 • K+: [Ar] 4s0 or just [Ar] • Ca: [Ar] 4s2 • Ca2+: [Ar] 4s0 or just [Ar] • Transition metal cations may have valence electrons left over and can form more than one oxidation number

  10. Electronic Configurations of Cations • Left over valence electrons fill 3d only • Group number gives number of valence electrons • Cation has (group number – oxidation number) electrons • Mn7+: group 7 and oxidation number 7 so has: • (7 – 7) = 0 electrons: [Ar](3d)0 • Mn2+: group 7 and oxidation number 2 so has • (7 – 2) = 5 electrons: [Ar](3d)5 • Ni2+: group 10 and oxidation number 2 so has • (10 – 2) = 8 electrons: [Ar](3d)8 • Ni3+: group 10 and oxidation number 3 so has • (10 – 3) = 7 electrons: [Ar](3d)7

  11. Electronic Configurations of Cations • To minimize repulsion between electrons, they occupy d-orbitals singly with until they have to pair up: • Mn2+: [Ar](3d)5 3d • Ni2+: [Ar](3d)8 3d • If the metal cation has unpaired electrons, the complex will be attracted to a magnet: paramagnetic

  12. Aqueous Oxoanions of Transition Metals • One of the most characteristic chemical properties of these elements is the occurrence of multiple oxidation numbers, often associated with different colours. Ion Ox. No. Colour VO3-+5 yellow VO2+ +4 green V3+ +3 blue V2++2 violet

  13. Colourful Complexes • Aqueous solutions of the Co(III) complexes (from left to right): [Co(NH3)5OH2]3+, [Co(NH3)6]3+, trans-[Co(en)2Cl2]+, [Co(en)2O2CO]+ and [Co(NH3)5Cl]2+. • All contain Co(III): colour influenced by the ligand

  14. Absorbed and Observed Colours Unless the d-orbitals are empty, half full or full, electrons can be excited from one d-orbital to another: absorption of light which we see as colour

  15. Summary: Complexes II • Learning Outcomes - you should now be able to: • Complete the worksheet • Work out the electron configurations of atoms and cations • Work out the number of unpaired electrons • Answer review problems 13.59-13.62 in Blackman • Next lecture: • The Biological Periodic Table

  16. Practice Examples

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