Transition Metals and Aqueous ions Flashcards
What is a transition metal?
Transition metals are elements in the d-block with an incomplete d-subshell as an atom or ion
What are the 4 characteristic behaviours of transition metals?
complex formation (forms a molecule with ligands and a central metal ion)
formation of coloured ions
variable oxidation state
catalytic activity.
What is a ligand?
A ligand is a molecule or ion that forms one or more co-ordinate bond with a transition metal by donating a pair of electrons.
What is a complex?
A complex is a central metal atom or ion surrounded by ligands.
What’s a ligand substitution reaction?
When ligands swap in a chemical reaction.
Co-ordination number
The number of co-ordinate bonds to the central metal atom or ion in a complex
What’s useful about the overall charge of a complex?
Overall charge can be used to calculate the oxidation state of the metal by looking at the ligands present.
Monodentate ligands
Ligands that make one coordinate bond to a metal ion.
Monodentate ligands examples
NH3, H2O, and Cl- can act as monodentate ligands.
Cl- as a ligand
Cl-is much larger than the O in H2O and the N in NH3 so only 4 Cl- fit around a metal ion where as 6 H2O/NH3 fit around the metal ion.
Bidentate ligand
Ligands that can make two coordinate bonds to a metal. You need to know two examples, ethane-1,2-diamine and ethanedioate.
Bidentate ligands example
ethane-1,2-diamine (H2NCH2CH2NH2)and ethanedioate. (C2O42–)
Multidentate and examples
Ligands that can make more than 2 coordinate bonds to a metal. You need to know EDTA4- and Haem is on the data sheet.
Drawing bidentate ligand with 3 NH2CH2CH2NH2
Drawing bidentate ligand with 3 C2O4 2-
what determines the shape complexes?
Square planar is caused by having a d8 electron configuration.
A complexes’ shape depends on their coordination number:
2 Coordination number ligand shape and bond angle?
Linear, 180 degrees
4 coordinate - non d8 metal shape and bond angle
Tetrahedral, 109.5
4 coordinate - d8 metal shape and bond angle
Square planar, 90 degrees
6 coordinate shape and bond angle
Octahedral, 90 degrees
What is cis-trans isomerism?
Cis-trans isomerism (similar to E/Z isomers) occur when there are only 2 of one specific monodentate ligand (other ligands can be any type of ligand). The trans isomer the 2 ligands of the same type are 180 degrees away and the cis isomer they are 90 degrees away.
Bidentate ligands in complexes with 2 monodentate ligands can also exhibit cis-trans isomerism
What’s cis platin? how does it funciton?
Cisplatin has the structure pictured.
Cis platin the Cl- ligands can be replaced by guanines to bind DNA together.
Optical isomers in complexes
Complexes that contain 2/3 bidentate ligands or a multidentate ligand exhibit optical isomerism (non-superimposable mirror image
What is Haemoglobin? How does it work?
Haem is an iron(II) complex with a multidentate ligand.
Oxygen forms a co-ordinate bond to Fe(II) in haemoglobin, enabling oxygen to be transported in the blood.
Carbon monoxide is toxic because it replaces oxygenco-ordinately bonded to Fe(II) in haemoglobin and this coordinate bond is stronger then Fe-O2 so removes this haem from reactions.
Ligand substitution reactions
Ligands when added to a solution containing complexes will substitute,
This is powered by entropy creating disorder.
When does complete substitution occur?
When a 4 coordinate complex is formed or a multidentate ligand is added
When does partial ligand substitution occur?
With an excess of ammonia being added to copper 2+ ions,
When told in the question
Model Answer - Chelate effect
When ligands that form more coordinate bonds are substituting
The overall enthalpy change is negligible as the number and type of bonds are similar
There is a significant increase in entropy as the total number of particles increases. (In the reaction above from 4 aqueous particles to 7 aqueous particles.)
This makes the reaction have Gibbs’ free energy change negative so this is highly favoured by entropy and the product is very stable
These ligands can only be substituted by ligands that form more or same number coordinate bonds (mono<bi<multi)
How does colour arise?
A portion of visible light of particular frequencies are absorbed to excite d electrons to higher energy levels in the split d orbitals. The frequencies of light that are not absorbed are transmitted to give the substance colour (absorbs opposite colours).
Why are compounds not coloured?
Compounds without colour occur because they have completely filled/empty d subshells so can’t absorb visible light
What effects the size of the energy gap/colour of the complex?
Colour changes arise from changes in
1. oxidation state
2. co-ordination number
3. ligand
This is because it alters the size of the energy gap
What’s the equation to calculate the size of an energy gap in a complex?
ΔE=hv=hc/λ
v =frequency of light absorbed (unit s-1or Hz)
H = Planck’sconstant6.63×10–34(J s)
ΔE=energy gap between split orbitals (J)
c = speed of light (3.00 x 10^8(m s–1)
λ= wavelength of light absorbed (m)
What is colorimetry? What practical steps need to be taken?
Colorimetre is a machine that can be used to measure the amount of light being absorbed.
The amount of light absorbed is proportional to the concentration of the solution.
Sometimes the colour change may be hard to detect so a colour intensifying ligand like bipy is added.
How do you create a calibration curve/graph for colorimetry? (model answer)
Measure absorbance for a range of known concentrations
Plot graph of concentration vs absorbance
Read value of concentration for the measured absorbance from this graph