unless otherwise stated, all images in this file have been reproduced from: blackman, bottle,...
Post on 31-Mar-2015
221 Views
Preview:
TRANSCRIPT
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
Slide 2/14
e CHEM1002 [Part 2]
Dr Michela SimoneLecturer
BSc (I Hons), MSc, D.Phil. (Oxon), MRSC, MRACI
Weeks 8 – 13
Office Hours: Monday 3-5, Friday 4-5Room: 412A (or 416)
Phone: 93512830e-mail: michela.simone@sydney.edu.au
Slide 3/14
e
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
Summary of Last Lecture
Slide 4/14
e
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
Complexes III
Slide 5/14
e Transition (or d-block) Metals
Slide 6/14
e Electronic Configurations of AtomsIn 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
4s
3d
ener
gy
Slide 7/14
e 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
Slide 8/14
e 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!)
Slide 9/14
e Electronic Configurations of Cations• To minimize repulsion between electrons, they occupy d-
orbitals singly with parallel spins until they have to pair up:
3d
Mn2+: [Ar](3d)5
3d
Ni2+: [Ar](3d)8
• If the metal cation has unpaired electrons, the complex will be attracted to a magnet: paramagnetic
Slide 10/14
e 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
Slide 11/14
e 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
Slide 12/14
i 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
Slide 13/14
e 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
Slide 14/14
x Practice Examples
1. How many d-electrons and how many unpaired electrons are there in the following complexes?
A.K2[NiCl4]B.[Co(en)3]Cl3C.[CrCl2(OH2)4]+
D.K2[Zn(OH)4]E.[PtCl2(NH3)2]
2. Consider the compound with formula [CoCl2(NH3)4]Br2H2O
(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?
top related