Transition Metals Flashcards
What is a transition metal?
a transition metal has an incomplete d sub-shell either as an element or either as one of it’s common ions
where on the periodic table are transition metal?
D Block - large central block of the periodic table
what does this definition mean?
this definition means that not all the elements or ions of metals in the D-block can be considered as
what are the 4 characteristic properties of the transition metals?
- the formation of complexes
- the formation of coloured ions
- variable oxidation states
- catalytic activity
what are the characteristics of all transition metals the result of?
the result of their electronic structure (incomplete d sub-shell in atoms or ions)
How many electrons can the 3d sub shell hold?
10 electrons
3d elements are the first…?
10 elements in the first row of the d-block
which of the first 10 elements have a abnormal electronic structure/ deviate from the pattern?
- chromium
- copper
Draw the structure of the first row of transition metal atoms
how can we abbreviate electron structure?
using elements zero
why are the electron structures of chromium and copper slightly different?
chromium has the structure [Ar] 4s1 3d5 rather than [Ar] 4S2 3d4. This is because having a half-filled sub-shell (d5) gives it extra stability (same for copper)
why is Cu2+ considered a transition metal and not Copper?
- the structure of copper does not have an incomplete d sub-shell However cu2+ does have an incomplete d sub-shell, therefore cu2+ is a transition metal ion
why is zinc not classified as a transition metal
- the structure of copper does not have an incomplete d sub-shell However Zn2+ does have an incomplete d sub-shell, therefore Zn2+ is a transition metal ion
what ions do transition metals produce when they lose an electron?
positive ions
why are 4s electrons lost first before 3d electrons?
3d sub-shells are lower in energy than 4s therefore the 4S electrons are lost before the 3d electrons
which two ions are non-transitional and why?
Sc3+ and Cu+ because they do not have an incomplete d sub-shell
what do transition metal compounds not have?
do not have transition metal ions with outer-s-electrons
what gives transition metal ions their properties?
the ions have an incomplete d sub-shell and it is the arrangement that gives the ions their characteristic properties
Explain, In terms of electronic structures of their ions, why a solution of iron (II) is rapidly oxidised to iron (III).
- Iron (II) has the electronic structure of [Ar] 3d6 and Iron (III) has the electronic structure [Ar] 3d5
- iron 3 has a half-filled d sub shell, so has extra stability
Complex Formation
what does a complex consist of?
a complex consists of a central transition metal ion or atoms surrounded by ligands
What is a ligand?
Ligands is a species that donates a lone pair of electrons to the metal ion and form co-ordinate bonds (dative)
Ligand = Lewis base = Nucleophile
what is the co-ordinate bonds formed by?
State what the Transition metal ion and the ligand act as?
is formed by the overlap of a ligand orbital (containing a lone pair of electrons) with a vacant orbital on the transition metal ion.
Transition metal acts as a Lewis Acid = electron pair acceptor
Ligand acts as a Lewis Base = electron pair donor
What is a complex?
a complex consists of a central transition metal ion surrounded by ligands
what is the co-ordination number?
the co-ordination number of a complex is the number of atoms bonded to the central metal ion
the co-ordination number differs from it’s oxidation state when..?
in a complex compound
in other words,..?
the number of atoms bonded to the central atom is more than the normal bond forming ability of the metal
what is usually the co-ordination number?
2, 4 or 6 (coordinate bonds formed)
what does the co-ordination number determine?
determines the shape of the complex
what appearance does Anhydrous copper sulphate (II) (CuSO4) take normally?
White solid
Anhydrous copper sulphate forms what colour in water?
blue (solution)
why does Anhydrous copper sulphate turn blue when reacted with water?
this is because the Cu2+ ions get surrounded by water molecules that bond to the Cu2+ ion
what complex ion is formed?
[Cu(H2o)6]2+ - Hexaaquacopper(II) ion
Draw the complex ion, Hexaaquacopper (II)
what do water molecules act as?
ligands
how many atoms (water) are bonded to the central atom?
therefore…?
6 - therefore the co-ordination number if 6
explain bonding in this complex ion?
each water molecule oxygen oxygen atom has donated 1 lone pair of electrons into a vacant orbital on the Cu2+ ion to form a co-ordinate bond
draw a word equation to show the formation of Hexaaquacopper (II)
CuSO4 —- H2O—–> [Cu(H2O)6]2+
what is the co-ordination number and the oxidation state of Copper?
co-ordination number = 6
oxidation state = +2
what is this reaction the test for?
test for water
Naming complex ions
1st part of the name =
second part of the name =
third part of name =
4th part of the name =
- number of ligands
- ligand
- metal
- oxidation state of the metal
what type of ligand is water?
water is a neutral ligand
what does this mean?
the overall charge on the complex ion is the same as the charge on the central metal ion
Give an example for a complex ion where the charge on the ligand is taken into account
tetrachlorocuprate (II) ion [Cu(Cl)4]2-
what oxidation sate does Na+, K+, and Ag+ have?
+1
what oxidation state does Mg2+, Ca2+, Ba2+ have?
+2
what oxidation sate does F-, Cl-, I- have?
-1
what oxidation state does O2- and S2- have?
-2
the oxidation state of the central atom in a complex ion is the charge…?
it would have if it was a simple ion (not bonded to other species)
what will the sum of the oxidation states in a neutral compound be?
zero
How does this differ for charged ions?
the sum of the oxidation state in an ion is equal to the overall charge of the ion
what are the following ligand charges:
water =
ammonia =
hydroxide ion =
chloride =
cyanide ion =
water = zero
ammonia = zero
hydroxide ion = -1
chloride = -1
cyanide ion = -1
calculate the following oxidation states of the metal ion:
1. [MnO4-]-
2. [VO3]-
3. [Cr2O7]2-
4. [Agcl2]-
5. [Cu(NH3)4(H2O)2]2+
6. [Ag(CN)2]-
- Mn=+7
- V = +5
- Cr = +6
- +1
- +2
- +1
How does the name of the ligand change when they’re in a complex?
- Water changes to Aqua
- Chloride changes to Chloro
- Ammonia changes to Ammine
what are the prefixes for each ligand?
Di, Tri, Tetra, Hexa
How does the metal ion’s name change when it forms a negatively charged complex:
silver =
Copper =
iron =
manganese =
Chromium =
Colbalt =
Vanadium =
silver = Argentate
Copper = Cuprate
iron = ferrate
manganese = manganate
Chromium = Chromate
Colbalt = Colbaltate
Vanadium = Vanadate
Name the following compounds:
1. [Cu(H2O6]2+
2. [CoCl4]2-
3. [Cr(NH3)6]3+
4. [Ag(NH3)2]+
- Hexaaquacopper(II)
- tetrachlorocolbaltate (II)
- Hexaamminechromium (III)
- Diamminesilver(I)
Different types of Ligand
what is a complex ion?
a complex ion consists of a central transition metal ion surrounded by ligands
what is a ligand?
A ligand is a species that donates one or more lone pairs of electrons to a metal ion (to form a co-ordinate bond)
How are Ligands classified?
ligands are classified by the number of co-ordinate bonds that they are bale to form in complexes (i.e the number of atoms that can donate a lone pair of electrons)
What are Monodentate ligands?
Monodentate ligands form one co-ordinate bond to the central metal ion (i.e one atom from the ligand donate one lone pair of electrons)
what does Monodentate mean?
‘single-toothed’ - one biting point
what are examples of Monodentate ligands?
H2O, NH3, CL-, OH-, CN-
Which two examples of Monodentate ligands are similar, explain why?
Both H2O and NH3 are similar in size (both small) and are both uncharged
In Monodentate ligands, the co-ordination number is equal to…?
the number of ligands attached to the central transition metal ion
Draw the complex ion:
- Hexaaquairon (II) ion
- Tetrachlorocolbaltate (II) ion
- Diamminesilver (I) ion
what is a bidentate ligand?
bidentate ligands form two co-ordinate bonds to the central transition metal ion (i.e the ligand has two electron pair donor atoms)
what are examples of Bidentate ligands? Draw each of the structures out?
- 1,2-diaminoethane H2NCH2CH2NH2 - bonds through 2 Nitrogens
- ethanedioate C2O4- - bonds through 2 oxygens
Draw the complex ion, where Chromium is the central transition metal ion, and three 1,2-diaminoethane ligands are bonded to the central metal ion. (Charge on the ion is 3+)
What is the co-ordination number of the above ligand?
There is only three ligands but the Co-ordination number is 6
what is a multidentate ligand?
multidentate ligands can form three or more co-ordinate bonds to the central transition metal ion (i.e the ligand has three or more electron pair donor atoms)
what can form the anion EDTA^4-?
Bis[di(carboxymethyl)amino]ethane or H4EDTA
how many bonds does EDTA^4- form?
forms 6 bonds with the metal ion
Draw the structure of EDTA4-, Highlight the 6 lone pairs!
Draw hoe EDTA4- surrounds the metal ion?
what ratio does the metal ion and EDTA ligand form?
1:1 complex - 1 metal ion and 1 EDTA ligand
what are the complexes formed called when Bidentate or Multidentate ligands bond to the central transition metal ion
Chelates
what does the word Chelate mean?
‘Crab claw’
why are Chelates more stable than Monodentate ligands?
Chelates are often more stable than Monodentate ligands since their formation results in an increase in entropy (an increase in system disorder)
what is this called?
The chelate effect
what is EDTA commonly used as?
as a chelating effect and it’s complex are extremely stable
Draw out the word equation to show how EDTA forms a very stable complex?
[Cu(H2o)6]2+ + EDTA4- ——> [Cu(EDTA4-)]2- + 6H20
in the above example, explain how this leads to chelate effect?
the formation of the chelate complex leads to an increase in entropy (more disordered system since more chemical species are formed - chelate effect.
what is the feasibility for all chemical reactions?
is a balance between the enthalpy change and the entropy change for the reaction (ΔG)
what is the dominant factor in the formation of EDTA complexes?
In the formation of EDTA complexes, the entropy change is the dominant factor
Uses of EDTA
what ability does EDTA have that makes it very useful?
has the ability to ‘trap metal ions’
what are the many uses of EDTA?
- used as an antidote to metal poisoning
- used in blood transfusions ans surgical operations to remove calcium ions which cause blood clotting
- used to remove calcium ions from hard water
How is EDTA able to act as an antidote for metal poisoning?
it can remove dangerous metal ions (e.g lead and mercury) from the blood (excreted as the stable EDTA complex)
Describe the effect of hardwater on pipes?
Hard water can lead to the blockage of water pipes and form scum on bathwater
what products contain EDTA and why?
EDTA removes calcium ions from hard water, therefore, many cleaning products contain EDTA e.g shampoo
Blood contains which metal Complex?
Iron(II) complex called Haem
What species of Ligand does Haem/iron complex (II) contains?
contains Multidentate ligand
How are atoms arranged around the Iron (II)?
octahedrally
How many atoms is bonded to the Iron in a plane?
The iron (II) is bonded to 4 nitrogen atoms in a plane
where do the four atoms come from?
they come from a porphyrin molecule
what is the Porphyrin molecule?
a large organic tetradentate ligand
what else is the iron bonded to?
the iron is also bonded to another nitrogen atom above the plane from a protein called globin
what is the final 6th position of the iron octahedral complex occupied by?
by an oxygen molecule (oxyhaemoglobin) or a water molecule
What bonds does Oxygen form to the iron (II) and what does this allow?
forms weak co-ordinate bonds. This allows Haemoglobin to transport oxygen around our bodies through the blood
what else can the final 6th position of Haemoglobin be occupied by?
Carbon monoxide
Why is carbon monoxide able to occupy the final 6th position?
Carbon monoxide form strong co-ordinate bond with the iron (II) than an oxygen molecule (carboxyhaemoglobin)
What is reduced when carbon monoxide is present in the blood?
When carbon monoxide is present in the blood, the oxygen-carrying capacity is greatly reduced.
Why is carbon monoxide toxic?
Carbon monoxide is toxic because it can replace oxygen co-ordinately bonded to Fe(II) in haemoglobin
Draw the structure of Oxyhaemoglobin
How to answer a question on Chelate effect? - try to find mark scheme answer!!
- formation of a VERY STABLE chelate complex
- leads to an increase in entropy
- give example e.g [Cu(H2o)6]2+ + EDTA4- ——> [Cu(EDTA4-)]2- + 6H20
- there 2 species at the start, 7 at the end = more disordered system = increase in entropy
Shapes of Complex ions
what is the most common Complex ion shape?
Octahedral - bond angle of 90°
what type of ligand forms Octahedral complex ions?
Monodentate ligands
what is the co-ordination number in an octahedral complex?
For monodentate ligands, how many ligands are there and how many co-ordinate bonds are formed ?
- in octahedral complex ions , co-ordination number is 6
- For monodentate ligands, this means that 6 ligands form 6 co-ordinate bonds to the central transition metal ion
what complex does the first row of transition metal ions form with water?
form Octahedral Hexaaqua ions
Draw the two main structure of the octahedral ion [Cu(H2O)6]2+
which two ligands usually form an octahedral shape and have a co-ordination number of 6?
Water and ammonia
why do water an ammonia usually form Complex containing a co-ordination number of 6 therefore an octahedral shape?
- water and ammonia are small ligands/ small in size
- therefore, 6 water and or ammonia can fit around the central transition metal ion
Draw octahedral complex [Fe(NH3)4(H20)2]2+
what is the second most common shape a complex ion forms?
Tetrahedral shape
what is the bond angle and co-ordination number of a tetrahedral complex?
Bond angle = 109.5 °
Co-ordination number = 4
what type of ligand form Tetrahedral complexes?
Monodentate ligands - large negatively charged ligands
How many Monodentate ligands will form bonds in a tetrahedral complex?
This means that 4 ligands can form 4 co-ordinate bonds to the central transition metal ion
Give examples of the type of Ions that form complexes tetrahedral in shape?
- Chloride ions
- Bromide ions
- Iodide ions
why can chloride only form 4 bonds whereas ammonia and water can form 6?
- Chloride ion ligands are larger than water and ammonia
- Therefore, there is only space for 4 chloride ion ligands around the central transition metal ion
why are chloride ions further apart in the tetrahedral arrangement than they are in an octahedral arrangement?
because there is less electron cloud repulsive forces between ligands
Draw the tetrahedral complex [CuCl4]2-
why don’t fluoride ions form tetrahedral complex but form octahedral complex instead?
Fluoride ions ligands are smaller than Chloride ion ligands
what are less common complex shapes?
- square planar = Bond angle of 90°
which Important molecule has a square planar complex?
CISPLATIN
what is cisplatin?
Cisplatin is a Anti-Cancer drug used in Chemotherapy
what type of cancer has it been used to treat?
Lung and bladder
what type of complex does Cisplatin form, How many bonds?
Cisplatin is a 4 co-ordinate, square planar complex of Platinum (II)
what are the two ligands present in the molecule?
2 chloride ions (CL-) ligands and 2 NH3 ligands
Draw the structure of Cisplatin.
What is cancer caused by?
cancer is caused when cells mutate and start dividing uncontrollable to form tumours
in order for a cell to divide, what needs to happen?
DNA needs to replicate - so the two strands of DNA have to unwind so they can be replicated/copied
How does cisplatin effect this (DNA replication)?
Cisplatin stops this happening properly(stops DNA replication), so that tumour cells stop reproducing and cancer cells can not longer divide and grow/replicate
what type of reaction occurs between the ligands and Cisplatin?
Cisplatin does a ligand replacement reaction with DNA in which a co-ordinate bond is formed between platinum and a nitrogen atom on guanine
Draw How cisplatin undergoes a ligand replacement reaction with DNA, until
- the nitrogen atom on guanine can bond to the platinum and replace the chloride
- a second nitrogen atom from a nearby guanine molecule (on the same strand or on the other strand) can bond to the platinum and replace the second chloride too
These cisplatin complexes cause the strands to..?
Kink - they can’t unwind and be coiled properly - so they can’t replicate properly
what is a downside of Cisplatin?
- cisplatin can bind to DNA in normal cells as well as cancer cells - so healthy cells can be prevented from dividing too
- so causes problems for healthy cells that replicate frequently e.g hair + blood cells
- therefore, cisplatin has serious risks associated with it’s use and a number of TOXIC side effects
what are common side effects of using cisplatin?
- kidney damage, nerve damage, hearing loss, nausea, vomiting, alopecia and electrolyte disturbances
How can we reduce the effect of side effects?
- lowering the dosage and also using methods that can help deliver the drug directly to the tumour
so what does society/chemists need to asses the balance..?
society needs to asses the balance between the benefits and the adverse effects of drugs, such as the anti-cancer drug cisplatin
even though cisplatin has many side effects it’s use is widespread, why?
Cisplatin’s use is widespread in medicine since the balance of long-term positive effects (curing cancer) outweigh the negative short-term side effects
Draw the structure of Transplatin
(chlorides are on the opposite sides of the complex to each other)
How is Cisplatin different to Transplatin
has different biological effects to cisplatin
what complexes have a bond angle of 180°?
Linear complexes