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] Dr Michela Simone Lecturer BSc (I Hons), MSc, D.Phil. (Oxon), MRSC, MRACI Weeks 8 – 13 Office Hours: Monday 3-5, Friday 4-5 Room: 412A (or 416) Phone: 93512830 e-mail: michela.simone@sydney.edu.au It is a good idea if all lecturers can make an appearance for the first lecture. Remind students we are IT for the rest of the semester. DEMOS for this lecture: EXP 2.3: “Charles law (2.3), EXP 2.1 “CO2 density (2.1)

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 bidentate ligands, optical isomerism is also possible Metal complex formation can greatly increase solubility

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

Transition (or d-block) Metals

Electronic Configurations of Atoms In 4th row, 4s and 3d orbitals are available for electrons There is one 4s orbital: it can accommodate 2 electrons There are five 3d orbitals: each can accommodate 2 electrons, giving a total of 10 electrons Fill 4s then 3d energy 3d 4s

Atomic Configurations Fill 4s then 3d Group number gives number of valence electrons Electronic configurations: K: group 1 so [Ar](4s)1(3d)0 Sc: group 3 so [Ar](4s)2(3d)1 Mn: group 7 so [Ar](4s)2(3d)5 Ni: group 10 so [Ar](4s)2(3d)8 Zn: group 12 so [Ar](4s)2(3d)10 [Ar](4s)x(3d)y where x + y = group

Electronic Configurations of Cations 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 (4s always empty!) Demo 6.5 - Fe/Mn reaction

Electronic Configurations of Cations To minimize repulsion between electrons, they occupy d-orbitals singly with parallel spins until they have to pair up: Mn2+: [Ar](3d)5 3d Ni2+: [Ar](3d)8 3d Demo 6.5 - Fe/Mn reaction If the metal cation has unpaired electrons, the complex will be attracted to a magnet: paramagnetic

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

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 Blackman, Bottle, Schmid, Mocerino & Wille (2007). Wiley & Sons: FIGURE 13.19 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+. As the metal ion is the same in all cases, the variety of colours arises from the different ligands surrounding the Co(III) ion.

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

Summary: Complexes II Complete the worksheet 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

Practice Examples How many d-electrons and how many unpaired electrons are there in the following complexes? K2[NiCl4] [Co(en)3]Cl3 [CrCl2(OH2)4]+ K2[Zn(OH)4] [PtCl2(NH3)2] 2. Consider the compound with formula [CoCl2(NH3)4]Br2H2O (i) Write the formula of the complex ion. (ii) Write the symbols of the ligand donor atoms. (iii) What is the d electron configuration of the metal ion in this complex?