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CHEM1010 Transition Metal Chemistry

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CHEM1010
TRANSITION METAL CHEMISTRY
Dr Philip Sharpe CHEMISTRY EMAIL p.sharpe@uq.edu.au

PHONE 3365 3900 Room 205 Chemistry

CHEM1010 Transition Metal Chemistry

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Associate Lecturer at UQ since 2010. Im the academic in charge of the first year Chemistry laboratory. I also coordinate CHEM1021 and teach second year biological inorganic chemistry in CHEM2052. My research interests are in the area of chemistry education and coordination chemistry applied to medicine.

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Figures in these lectures notes are taken from Blackman, 2nd Edition, and are used with permission from the publishers and distributors John Wiley
This section of the lecture course deals with material covered in Chapter 13 of Blackman Chemistry. Note: First edition cannot be used for inorganic nomenclature section. These notes are incomplete and require you to add material.
CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences

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CHEM1010 Transition Metal Chemistry

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CHEM1010 Transition Metal Chemistry

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Why is this stuff (transition metal chemistry) important?

Note: This first section on why transition metals are important is not examinable.
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Ruby is an aluminium oxide (Al2O3) crystal in which some of the aluminium atoms have been replaced with chromium atoms. Chromium gives ruby its characteristic red colour.
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http://www.llnl.gov/nif/library/aboutlasers/how.html

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Chromium is responsible for the lasing behavior of the crystal. Chromium atoms absorb green and blue light and emit or reflect only red light.
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Metal Ions in Biology

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Worldwide prevalence of anaemia 1993-2005, WHO Global Database on Anaemia


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Essential Transition Metals Vanadium Manganese

Biological Function

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Essential for rats and chickens. No specific role known in humans. Needed for several enzymes, e.g. Mn superoxide dismutase, glutamine synthetase. Hemoglobin, myoglobin, other enzymes Vitamin B12 Urease (plants), hydrogenase (bacteria) Found in several enzymes. Cu-Zn superoxide dismutase detoxifies free radicals. Bound to insulin, around 10% of all proteins contain Zn. Component of redox enzymes e.g. sulfite oxidase.
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Iron Cobalt Nickel Copper

Zinc Molybdenum (only essential 2nd row transition metal)


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hemoglobin (Hb) - a tetrameric protein O2 uptake in the lungs and transport in the blood stream. 65% of the iron present in a human.

Other iron proteins involved in DNA synthesis, drug metabolism, energy pathways and many other functions.
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The organic core of hemoglobin

Porphyrin

Heme (Porphyrin + iron)


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http://www.chemistry.wustl.edu/~edu dev/LabTutorials/Hemoglobin/chang emovie.html

A heme site in hemoglobin


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DINITROGEN - thermodynamically stable, so reduction requires a large amount of energy. N2 + 10H+ + 8e- 2NH4+ + H2 In the Haber Process, N2 and H2 gases are reacted over an Fe3+ catalyst in which Al2O3 and K2O are used as promoters. The reaction is carried out under conditions of 250 atm, 450-500 C; resulting in a yield of 10-20%: N2(g) + 3H2(g) 2NH3(g) H = -92.4 kJ mol-1

The Haber process produces 100 million tons of nitrogen fertilizer per year, mostly in the form of anhydrous ammonia, ammonium nitrate and urea. 1% of the world's annual energy supply is consumed in the Haber process. That fertilizer is responsible for sustaining 50% of the Earth's population.

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How Nature does it:-

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Rhizobium bacteria, which live in legume root nodules contain nitrogenase protein. MoFe7S8
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Science 334, 974 (2011) DOI: 10.1126/science.1206445 Kyle M. Lancaster, et al. X-ray Emission Spectroscopy Evidences a Central Carbon in the Nitrogenase IronMolybdenum Cofactor CARBON!!!!!!!!!!!!!!! Starts out as a methyl group in Sadenosylmethionine the process is still being investigated. J. A. Wiig, Y. Hu, C. C. Lee, M. W. Ribbe, Science 337, 1672 (2012).

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Metal ions in Medicine cis-[Pt(NH3)2Cl2] cisplatin; an anticancer drug Radionucleotides 64Cu for tumour imaging Antiarthritic drugs gold complexes Metal ions in Industry Catalysts e.g. - Optically active metal complexes as agents for synthesis of chiral pharmaceuticals. - catalytic converters in cars for removal of nitrogen oxides from exhaust (Rh, Pt, Pd).

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We are at a wonderful time for chemistry. It is, I believe, in the position of physics in the 1910s, just before quantum mechanics made the world impossibly strange, or biology in the 1950s, just before the double helix obliterated the old biology. George M. Whitesides Priestley Medal Address, 2007.

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CHEM1010 Transition Metal Chemistry

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Blackman p 138, 546

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The Aufbau Principle allows us to write electron configurations

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Blackman p 545-546

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Transition metal atoms:characterised by d valence orbitals (e.g. 3d, 4d, 5d)

neutral atoms generally have valence electron configurations of (n+1)s2nd(x-2) (x is the group number of the metal in the periodic table, n is the principal quantum number) e.g. Vanadium, group number of 5, electron configuration [Ar]4s23d3.

IUPAC definition: A transition metal is "an element whose atom has an incomplete d sub-shell, or which can give rise to cations with an incomplete d sub-shell". http://goldbook.iupac.org/T06456.html Zn, Cd, Hg (Group 2B elements) are d-block metals, but we can think of them as honorary transition metals because of their similar chemistry.
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The five 3d orbitals means a maximum of 10 d electrons. Two orbitals lie on axes, three orbitals lie between axes.

It is all about the d-orbitals & d-electrons!!!


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for example, element Ni (Z = 28); group 10


1s2 2s2 2p6 3s2 3p6 4s2 3d8

Remember from Module 1: Quantum numbers orbitals. All 3d orbitals are degenerate (equal in energy) in the elements and ions in the gas phase.

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Sc Ti V Cr Mn Fe Co Ni Cu Zn

21 22 23 24 25 26 27 28 29 30

1s2 2s2 2p6 3s2 3p6 4s2 3d1 1s2 2s2 2p6 3s2 3p6 4s2 3d2 1s2 2s2 2p6 3s2 3p6 4s2 3d3 Cr and Cu dont follow the regular pattern. The 4s and 3d orbitals in atoms are close in energy, so the lowest energy configuration has the 4s orbital halffilled and the 3d orbitals half-filled (Cr) or completely filled (Cu).

1s2 2s2 2p6 3s2 3p6 4s1 3d5 1s2 2s2 2p6 3s2 3p6 4s2 3d5 1s2 2s2 2p6 3s2 3p6 4s2 3d6 1s2 2s2 2p6 3s2 3p6 4s2 3d7 1s2 2s2 2p6 3s2 3p6 4s2 3d8 1s2 2s2 2p6 3s2 3p6 4s1 3d10 1s2 2s2 2p6 3s2 3p6 4s2 3d10

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Blackman, p 546

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Oxidation States

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Transition metals are typically found in various oxidised forms i.e. they can lose one or more electrons to form cations. Fe Fe2+ + 2eFe Fe3+ + 3e-

The chemical and physical properties are extremely dependent on the oxidation state (colour, reactivity, structure). The electrons that are lost come from the 4s orbital first, before the 3d orbitals. Remember that these orbitals are close in energy in atoms in the gas phase, and they swap relative energy levels in ions compared to the atoms. IMPORTANT!!!

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p. 546 Blackman 2nd ed.

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= common oxidation states


Table 13.1, p. 546 Blackman 2nd ed.

For ions in the same oxidation state, the number of d electrons increases going across the row from left to right. For the same element, the number of d electrons decreases as oxidation state increases. Elements in the middle have the greatest number of possible oxidation states.
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The higher oxidation states are limited by: The effective nuclear charge it becomes energetically unfavourable to remove more electrons. The number of d electrons. The intermediate oxidation states are often unstable due to disproportionation reactions leading to more stable reduced and oxidized forms. 2Mn3+ Mn2+ + Mn4+ Low oxidation states are unstable due to spontaneous oxidation by air. 2Cr2+ + O2 + 2H+ 2Cr3+ + H2O2

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An Aside:- Ionization Energy The ionization energy of an element is defined as the energy change when an electron is removed from an atom in the gas phase. For an element M the ionization energy (I1) is the energy change in the process M(g) M+(g) + e (I1) (kJ mol-1) And M+(g) M2+(g) + e (I2) (kJ mol-1) M2+(g) M3+(g) + e (I3) (kJ mol-1)
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Gas phase ionisation energies for the first row TM elements


4000 3500 3000 2500
Ionisation Energy 2000 (kJ mol-1)

1500 1000 500 0

1st Ionisation energy 2nd Ionisation energy 3rd Ionisation energy Sc Ti V Cr Mn Fe Co Element Ni Cu Zn

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The number of d electrons of transition metal ions


The electrons that are lost from first-row TM atoms to form ions come from the 4s orbital first, before the 3d electrons are lost.
(5s and 4d in the case of second row transition metals)

In transition metal chemistry we are often interested in knowing the number of d electrons (not least for exam questions). Easiest way is to count them using the Periodic table. For a divalent (2+) transition metal ion, the two 4s electrons are lost and then we just count along the row starting from scandium, the first transition metal.
1 2 3 4 5 6 7 8 9 10

(For Cr2+ and Cu2+ ions, the one 4s electron will be lost and one 3d electron.)
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Alternative method: Number of d-electrons = Number of electrons in ion number electrons in last noble gas element.

Ni2+ : Ni Z=28, so a Ni2+ ion has 28 - 2 = 26 electrons Last noble gas was Ar (Z=18). No. of 3d electrons = 26 -18 = 8 electrons
1s2 2s2 2p6 3s2 3p6 3d8

Really important!!!! 6/18 TM questions in last years exam required knowledge of the number of d-electrons.
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Divalent first row metal ions


Atomic Number

21

22

23

24

25

26

27

28

29

30

Element

Sc Ti

Cr

Mn Fe Co Ni

Cu Zn

Ionic Charge

2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+

d electron Config.

d1

d2

d3

d4

d5

d6

d7

d8

d9

d10

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What about TM ions with oxidation states other than II? Example: Co3+ This will have one less d-electron than Co2+ (or 3 less electrons than Co)
1 2 3 4 5 6 7 8 9 10

Co2+ has 7 d electrons, so Co3+ will have 6 d electrons. Alternately, Co (Z=27), so Co3+ has 27 - 3 = 24 electrons. Ar (Z=18) was the last noble gas, so number of d electrons = 24 -18 = 6 d electrons.

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Which two commonly occurring first-row transition metal ions have FIVE 3d electrons? A. B. C. D. E. Co3+ and Ni2+ Fe2+ and Co3+ V5+ and Cr6+ Mn2+ and Fe3+ Co4+ and Ni5+

Blackman worked example 13.1, p 546


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Coordination Chemistry
d-block metal ions are Lewis acids and they form compounds with Lewis bases. Lewis bases donate electron pairs. Lewis acids (e.g. d-block metal ions) accept electron pairs. The Lewis base donates an electron pair to the metal ion. The Lewis bases that are bonded to the metal ion in this way are called ligands. ([From Latin ligandus, to bind) The compound formed by a metal ions and its ligands is called a complex.
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Blackman p 552

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Coordinate Bonding
Transition metal ions form special type of bonds with other molecules/ions called coordinate bonds May be described as a Lewis acid-base reaction. Lewis acid: electron pair acceptor the metal ion. Lewis base: electron pair donor the ligand.

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Consider BF3 (B not a transition metal, example only) B 1s2 2s2 2p1 3 valence electrons F B F F BF3 has properties consistent with a Lewis structure with 3 B-F single bonds 6 electrons around the B.
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H H N H

F B F F

H N B F H F

Both electrons in the B-N bond are contributed by N. This is a coordinate covalent bond N
Lone Pair

B N B
empty orbital

Coordinate bonds are normal two electron bonds.


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LIGANDS
Complex or complex ion

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Any atom within a molecule or ion bearing a lone pair of electrons can potentially coordinate to a metal ion. NH3 can use the lone pair of electrons on the N to coordinate.
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The coordinated atom is known as the donor atom.

Ligand Metal ion

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Blackman p 547-551

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A metal ion can have several donor atoms coordinated at the same time.

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Blackman p 547-551

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LIGANDS

Dentate = having teeth

A monodentate ligand NH3 Other common monodentate ligands are F-, Cl-, Br-, I-, H2O.

Octahedron

An octahedral ligand arrangement


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Denticity The number of donor groups from a given ligand attached to the same central atom.
bidentate tridentate tetradentate pentadentate hexadentate = interacts with a metal through two donor atoms = interacts with a metal through three donor atoms = interacts with a metal through four donor atoms = interacts with a metal through five donor atoms = interacts with a metal through six donor atoms

Very much a connotation of holding on, e.g. teeth

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Blackman p 547-551

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Chelate (Chelation (from Ancient Greek , chel, meaning claw) Ring A bidentate ligand A bidentate ligand 1,2-diaminoethane pentane-2,4-dionato or or acetylacetonato ethylenediamine or acac

5-membered chelate ring


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6-membered chelate ring


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Blackman p 553

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monodentate

chelate (bidentate)

compare

en = 1,2-diaminoethane
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Name of ion or molecule


ethylenediamine Propane-1,3diamine 2,2-bipyridine 1,10phenanthroline Pentane-2,4dionate ion oxalate 1,4,7triazaheptane

Formula

Name of coordinated ligand


1,2-diaminoethane (ethylenediamine) Propane-1,3diamine 2,2-bipyridine 1,10-phenanthroline

Abbreviation Example

en pn bipy phen

[Ni(en)3]2+ [Co(pn)3]3+ [Ru(bipy)3]2+ [Ru(phen)3]2


+

Pentane-2,4-dionato acac oxalato 1,4,7-triazaheptane

[Co(acac)3] K3[Cr(ox)3] [Co(dien)2]3+

ox2dien

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Ethylenediaminetetraacetic acid

a polydentate ligand - EDTA

[Co(EDTA)]CHEM1010 Transition Metal Chemistry

Fig 13.6, p. 548 Blackman


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Blackman p 549-550

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Multidentate ligands can have the same or mixed donor atoms (e.g. EDTA).

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Ligands can be linear, branched, cyclic or bicyclic.

Ligands can potentially bridge two or more metal centres.


[Cu2(H2O)2 ( -OOCCH3)4] Figure 13.7, Blackman 2nd ed.

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Blackman p 551

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Many different types of ligands!!!

C5H5- ligand, an example of an organometallic ligand where C atoms are bound to the metal. The complex has the nickname ferrocene.

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Ligand design is important in the development of new materials for the capture and storage of CO2 and hydrogen. - new medical diagnostic agents. - new drugs to target metalloenzymes. - improved catalysts.

Science 329 (5990) 424-428 (2010) DOI: 10.1126/science.1192160


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Dr Vamvounis consultation drop-in session on organic chemistry; podium Friday May 24 from 10-12 Transition metal drop-in Friday May 24 from 2:10-4.

Quiz 3 available now!

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Blackman p 554

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Transition metal ions are the most common Lewis acids (electron pair acceptors) Combinations of transition metals and ligands result in a complex (a coordination compound) with a defined geometry.

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[Co(NH3)6]3+

Metal ion

Ionic charge
Note: There will be a counterion or ions balancing any charge but outside the complex ion. This is indicated by them being written outside the square brackets.

Complex or complex ion

Coordination number = count the number of donor atoms attached to the metal ion.
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Ligand
Coordination number = 6, as there are 6 N atoms coordinated.
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http://en.wikipedia.org/wiki/Hexamminecobalt %28III%29_chloride

Oxidation state of the metal ion is calculated by knowing Coordination number (= 6) The charges on the ligand (0) The type and number of counter ion (3 x Cl-, a monoanion) The overall charges must cancel: x + 3 x -1 = 0, so must be Co(III) = Co3+.
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Summary of Metal Complexes:

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Contain coordinate covalent bonds. Lewis acid-base adducts. Composition: central metal ion+ligands+counter ion/s (if needed) Called a complex ion if charged. Coloured, often with unusual magnetic properties e.g. [Cu(NH3)4]SO4 counterion (outside the Central ligands metal (inside the square brackets) ion square brackets)
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Consider CoCl3.nNH3 with n = 4, 5 or 6 4 different compounds are possible. How can we have these compounds with various compositions? Dissolve in water, add AgNO3. Some Cl precipitates as AgCl immediately, some more slowly; this difference indicates the number of Cl which are ionic (fast) and covalent (slow) CoCl3.6NH3 CoCl3.5NH3 CoCl3.4NH3 CoCl3.4NH3
Composition formula

[Co(NH3)6]Cl3 [Co(NH3)5Cl]Cl2 [Co(NH3)4Cl2]Cl [Co(NH3)4Cl2]Cl


covalent

yellow purple green violet


ionic

colour Number Cl precipitated

3 2 1 1

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Blackman p. 553

Coordination Geometries

Coordination number 2: collinear. Collinear complexes - common in the case of heavy metal cations of d10 electron configuration. [Au(CN)2] , formed during the extraction of gold from its ore, and [Ag(NH3)2]+ , formed when AgCl dissolves in ammonia solution. Coordination number 3: trigonal planar - quite rare; these complexes are found in instances in which ligands are large and steric repulsions are dominant, for example, [Pt{P(phenyl)3 }3]. Coordination numbers 7, 8, and 9: various Further types of coordination geometry exist for large cations, especially those of the 3+ lanthanide cations, for example, [La(edta)(H2O)3]-, [NbF7] 2 , [Mo(CN)8]4 , and [ReH9]2 .
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Coordination number 4:
tetrahedral - common for d10 metal ion species such as Zn2+ and Ga3+ , and d7 species, such as Co2+ . Examples: [ZnCl2(pyridine)2]; [GaCl4] ; and [CoCl2(4methylpyridine)2]. Square planar [Cu(NH3)4]2+ , also common for Ni(II), Pt(II), Ir(I), Rh(I) d8 systems. There is more space to fit ligands around a tetrahedral metal centre, so it is especially favoured for small metal ions with bulky ligands, as the ligands in a square planar complex will be closer together.
Note: Mistake p. 554 d10 metal ion should be Cu(I) not Cu(III). Cu(III) is d8.
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Blackman p. 554

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Coordination number 5: trigonal-bipyramidal and squarepyramidal - common in the case of complexes of metal ions of

coordination number 5. Examples: trigonal-bipyramidal complexes:[CuCl5]3, [Fe(CO)3(PF3)2], and [Mn(CO)4NO]. Examples: square-pyramidal complexes:[Ni(CN)5]3 and [Cu(hfacac)2(OH2)] . (hfacac = hexafluoroacetylacetonate)

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Coordination number 6: Octahedral Donor atoms at either (approximately) 90 (cis) or 180 (trans) to each other.
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Coordination compounds may exhibit isomerism, just like organic compounds (only better). (Do you remember this from the early organic chemistry lectures?)

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Isomerism in Coordination Compounds


Isomers (same formula, different properties) Structural isomers (different bonds, same molecular formula)
Linkage isomers (different atoms in the same ligand bound to the metal ion)

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Blackman p 555-558

Stereoisomers (same bonds, different arrangements)

Coordination sphere isomers

Geometric isomers

Optical isomers

Ionisation isomers

Hydrate isomers

Coordination isomers

cis and trans

fac and mer

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Blackman p 555-558

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Ionisation isomers

Interchange of counter ions and ligands. Physical properties are completely different.

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Blackman p 555-558

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Hydrate isomers

Results from the different numbers of water molecules that can be coordinated to a metal ion. A hydrate is formed when a crystal contains loosely held water molecules that are NOT coordinated to the metal ion. [Cr(OH2)6]Cl3 purple [Cr(OH2)5Cl]Cl2H2O blue-green green [Cr(OH2)4Cl2]Cl2H2O

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Blackman p 555-558

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Coordination isomers

- This form of isomerism results when ligands are exchanged between a complex cation and a complex anion of the same coordination compound.

[Co(NH3)6][Cr(CN)6]

[Cr(NH3)6][Co(CN)6]

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Blackman p 555-558 Linkage isomers (which atom in a ligand is bound to the metal ion)

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Requires two potential donors on the one ligand: e.g. NO2-, CN-, SCN-. These ligands are called ambidentate, as they have more than one potential donor atom.
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Blackman p 555-558

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Stereoisomers (same bonds, different arrangements)

Stereoisomers isomers with the same order of attachment of atoms, but a different orientation of their atoms in space.

Geometric isomers

cis and trans

cis-[Co(NH3)4Cl2]+ Two ligands at 90


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trans-[Co(NH3)4Cl2]+ Two ligands at 180


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Blackman p 555-558

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Geometric Isomerism

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cis-[Pt(NH3)2Cl2]

trans-[Pt(NH3)2Cl2]

Cisplatin is a chemotherapy drug that is given as a treatment for some types of cancer. It is most commonly used to treat testicular, bladder, lung, gullet, stomach and ovarian cancers. Trans isomer is inactive.
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Blackman p 557

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Geometric isomers

fac and mer

Look at the set of three ammine (NH3) ligands. All three NH3 ligands are: - on the same face of the octahedron. - cis (90) to each other. This is the facial isomer.

Facial (fac)
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Look at the set of three ammine (NH3) ligands. - All three NH3 ligands are coplanar with the metal ion and each other. - Two of the NH3 ligands are trans (180) to each other. One NH3 ligand is cis to the two others.
Meridion species of diatom (algae)

Meridional (mer)
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http://www.plingfactory.de/Science/Atlas/Kennkart en%20Algen/Diatomeen/Source/Meridion%20sp.. html

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fac-[Co(NH3)3Cl3]

mer-[Co(NH3)3Cl3]

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Facial isomer 3 ligands all cis to each other.

Meridional isomer 2 ligands trans to each other, one ligand cis to the two others.
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Stereoisomerism
Stereoisomers isomers with the same order of attachment of atoms, but a different orientation of their atoms in space. Optical isomers Enantiomers stereoisomers that are nonsuperimposable mirror images of each other.

Figure 17.10, p. 749 Blackman 2nd ed.


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Are these isomers of each other?

[Co(ox)3]3-

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Optical isomers - enantiomers

Are they mirror images? Yes!!


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Are they superimposable? No!! They are enantiomers, as they are non-superimposable mirror images. If you can rotate two structures so that they are identical then they are not isomers. If you have to break bonds to make them identical, they are isomers.
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Consider the following complex ion. Can this complex ion exist as optical isomers?
Yes it can

These are mirror images which cannot be superimposed.


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Consider the following complex ion: are cis and trans isomers possible?

1. Cis and trans isomers possible 2. Cis and trans isomers not possible

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cis (two optical isomers)

trans No optical isomers

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Can the following molecule exist in enantiomeric forms?

1. Yes it can exist as optical isomers 2. No it cannot exist as optical isomers


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Non-superimposable mirror images therefore they are optical isomers (enantiomers).

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Blackman p 558-560 2nd edition only

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RULES FOR NAMING METAL COMPLEXES


Look on the Blackboard page!!!!

(i) Cations are named before anions, with a space between the ions. This is the same rule that applies to other ionic compounds e.g. sodium chloride. (ii) The names of anionic ligands always end in the suffix -o. Ligands with names ending in ide, ite or ate have this suffix changed to ido, ito and ato, respectively. e.g. a chloride ion when bound to a metal is a chlorido ligand. a carbonate ion when bound to a metal is a carbonato ligand

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(iii) A neutral ligand is given the same name as the neutral molecule e.g. 1,2-diaminoethane Except: H2O Water becomes aqua NH3 Ammonia becomes ammine (Note: double m!!!) CO Carbon monoxide becomes carbonyl (iv) When there is more than one of a particular ligand, their number is specified by the prefixes di = 2, tri = 3, tetra = 4, penta = 5, hexa = 6. If the name of the ligand already incorporates one of these prefixes (e.g. 1,2-diaminoethane), enclose the ligand name in brackets and use the following prefixes instead bis = 2, tris = 3, tetrakis = 4. e.g. [Cu(en)2]Cl2 is bis(1,2-diaminoethane)copper(II) chloride NOT di(1,2-diaminoethane)copper(II) chloride.
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(v) In the name of the complex, the ligands are named first, in alphabetical order without regard to charge, followed by the name of the metal. Ignore the prefix in front if any. e.g. cis-[Pt(NH3)2ClBr] cis-diamminebromidochloridoplatinum(II) A B C

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(vi) Negative (anionic) complex ions always end in the suffix ate. The suffix is appended to the English name of the metal atom in most cases (or Latin stem for elements where the element symbol comes from Latin). If the name of the metal ends in ium or ese the ending is dropped and replaced by ate.
metal iron (Fe) copper (Cu) nickel zinc cobalt chromium manganese name in an anionic complex ferrate cuprate nickelate zincate cobaltate chromate manganate

Note: mistake p. 560 Blackman [CoCl2(NH3)4]- tetraamminedichloridocobaltate(III) ion


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(vii) The oxidation state of the metal is included in the name in parentheses in capital Roman numerals. Having this information included means that there is no need to specify the number of counter ions. K4[Fe(CN)6] K3[Fe(CN)6] potassium hexacyanidoferrate(II) NOT tetrapotassium hexacyanidoferrate(II) potassium hexacyanidoferrate(III)

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Blackman p 559
Name of ion or molecule Formula Name of coordinated ligand

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example

water ammonia Carbon monoxide Fluoride chloride Bromide iodide hydroxide methoxide cyanide

H2O NH3 CO FClBrIOHCH3OCN-

Aqua Ammine Carbonyl Fluorido Chlorido Bromido Iodido Hydroxido Methoxido Cyanido

[Cr(H2O)6]2+ [Co(NH3)6]3+ [Ni(CO)4] [TiF6]2[CoCl4]2[CoBr4]2[PtI4]2[Fe(OH)(H2O)5]2+ [Ti(OCH3)4] [Fe(CN)6]4School of Chemistry and Molecular Biosciences

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EXAMPLES: Look at the Blackboard pages on nomenclature (i) [Pt(NH3)4]Cl2 (ii) K4[Fe(CN)6] (iii) [Cr(OH2)4Cl2]Cl (iv) [Ni(en)3]Br2 tetraammineplatinum(II) chloride potassium hexacyanidoferrate(II) tetraaquadichloridochromium(III) chloride tris(1,2-diaminoethane)nickel(II) bromide

the prefix is tris (NOT tri); the ligand already has a multiple prefix (di-) in its name di- (bis-), tri- (tris-), tetra- (tetrakis-), penta- (pentakis-), hexa- (hexakis-)
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Name the following complex:[Ni(NH3)6](SO4) Hexaamminenickel(II) sulfate (or sulphate) Convert the following formula to a name:Na2[NiCl4] Sodium tetrachloridonickelate(II)
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Why are metal complexes coloured????????

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Experiment Four: How Sweet


Colourless aspartame complexes Cu2+(aq) to form a blue-coloured complex. The amount of complex formed is measured using a UV-vis spectrometer, enabling the concentration of aspartame in a sweetener sachet to be determined.

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Blackman p 565-570

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Crystal Field Model A simple approximation treats the coordinate bonds as electrostatic in origin. The ligand donor atom (the Lewis base) typically has a high electronegativity (N, O, P, S, halogen). The partial negative charge results in an electrostatic attraction to the positively charged metal ion.

H +

N H +

+ H
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Blackman p 566

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The five 3d-orbitals Two point along the axes dz2 dx2-y2

Three point between the axes dxy dxz dyz

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Blackman p 567

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1. 2.

In the free ion (no ligands) the five d-orbitals are of the same energy (degenerate). In the presence of the ligands (negative point charges) the d-orbitals split into two sets with different energies. dx2-y2 dz2 eg set higher energy dxy dyz dxz

In an octahedral complex . . .

3.

t2g set lower energy The degree and nature of the energy splitting depends on the coordination geometry and the type of ligands.
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Blackman p 567

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d-orbital splitting Octahedral complexes dz2 and dx2-y2 orbitals point towards the ligands (larger repulsion) so the energies are raised considerably dxy, dxz, dyz orbitals point between the ligands, the energies are essentially unchanged

2 eg orbitals 3 t2g orbitals

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Blackman p 569

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Tetrahedral complexes

dz2 and dx2-y2 orbitals point between the ligands (energies are virtually unaffected) dxy, dxz, dyz orbitals point towards the ligands, their energies are raised. This is the reverse of what occurs for octahedral complexes.
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http://www.dlt.n cssm.edu/tiger/ diagrams/comp lexions

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Blackman p 569

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Tetrahedral complexes

3 t2 orbitals 2 e orbitals
Tetrahedral

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eg

o
e

t2

t2g

Octahedral
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Tetrahedral
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Important that you understand and can use these diagrams!!!!

Blackman p 568

Electronic Configurations

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The most stable (ground state) d-orbital electronic configuration is a compromise between i. Occupying the lowest energy orbitals AND ii. minimising d electrond electron repulsion. The Pauli exclusion principle is still obeyed (maximum of 2 electrons per orbital, opposite spins). Assuming d-orbital splitting is small (weak field case) the electronic configuration is governed by Hunds rule (maximum number of unpaired spins), with orbitals filled from lowest to highest energy.
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d1

d2

Octahedral
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Tetrahedral
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d3

Octahedral
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Tetrahedral
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Tetrahedral
d4 d5

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d6

d7

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Tetrahedral
d8 d9

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d10

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Blackman p 568

Back to octahedral complexes . . . .

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No ambiguity in the way these (d1, d2, d3) orbitals fill

But for d4 - d7 there are two possibilities, depending on o size.


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Blackman p 568

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The energy difference between the t2g and eg sets of orbitals is relatively small weigh the energetic advantage of placing the 4th electron in a low energy t2g orbital against the energetic disadvantage that results from placing an electron in an already occupied orbital. This energy is called the spin pairing energy (P) The magnitude of P compared with o determines which electron configuration is favoured. If P>o then the energetically favourable electron configuration is that in which the 4th electron occupies an eg orbital (called a high spin configuration) If P<o the complex adopts a low spin configuration, that is paired with another electron in the t2g orbital.
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Blackman p 568

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high spin
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low spin
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high spin

d5

low spin

d6

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high spin

d7

low spin

d8

?
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d8

d9

d10

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Blackman p 572

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Spectrochemical series whether is big or small The magnitude of the d-orbital splitting (either o or t) is dependent on the type of ligand The (empirical) ordering of the ligands is governed by the ligand donor atom - It is known as the spectrochemical series the order of ligand field strength (representing a decrease in o) for common ligands is approximately
CN- > phen ~ NO2- > en > NH3 ~ py > H2O > C2O42- > OH- > F- > S2- > Cl- > Br- > I-

big o favours low spin


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small o favours high spin


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Blackman p 572

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Strong and Weak Field Ligands Hunds rule predicts the maximum number of unpaired (parallel) electron spins for a set of degenerate (or similar energy) orbitals Strong field ligands result in a large energy (o) difference between the dxy,dxz,dxy and dx2-y2 sets Weak field ligands result in a small energy (o) difference between the dxy,dxz,dxy and dx2-y2 sets
(Strong and weak field does NOT refer to the strength of the metal ion-ligand bonds, but to the size of o)
http://www.naomilkoffman.com/2012/03/25/theopposite-party/
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Blackman p 572

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CN- > phen ~ NO2- > en > NH3 ~ py > H2O > C2O42- > OH- > F- > S2- > Cl- > Br- > I-

low spin

high spin

Strong field e.g. [Fe(CN)6]3Vitally Important!!!!


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Weak field e.g. [Fe(H2O)6]3+

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Blackman p 568

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High and low spin complexes The most stable (or ground state) configuration is dictated by a compromise between: the electron occupancy of lower energy orbitals the inter-electronic repulsion

For d4 d7 electronic configurations there are two possible electronic ground states with either the . . . . - minimum number of unpaired electrons (low spin) OR - maximum number of unpaired electrons (high spin).
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Tetrahedral Complexes Unlike the octahedral complexes, low spin tetrahedral complexes are NOT found. Why? t = 4/9o (for the same type of ligands) Fewer donor atoms, and poorer overlap with d orbitals t is never large enough to enforce electron pairing

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Blackman p 574

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Magnetism

Both d6 systems, what are the differences between them?

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d6 system No unpaired electrons DIAMAGNETIC

d6 system 4 unpaired electrons PARAMAGNETIC

Remember: It is dia to have all paired electrons. Important terms!!!!!


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Magnetic Susceptibility balance

Gouy balance schematic. The weight of the sample in a glass tube is measured with or without a magnet present.
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REPELLED

ATTRACTED

DIAMAGNETIC
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PARAMAGNETIC
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Blackman p 574

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MAGNETISM The number of unpaired electrons (N) - the degree of interaction with magnetic fields We use a term called magnetic susceptibility, given by a numeric quantity called the magnetic moment (eff) or spin only magnetic moment (so)

eff = N ( N + 2)

B. M .

Important formula!!!!!! B. M. = Bohr magnetons This is on the data sheet for the exam.
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= eff
Number of unpaired electrons One Two Three Four Five

N ( N + 2) B. M .
eff B.M.

N is the number of unpaired electrons

1 (1 + 2) = 2 (2 + 2) = 3 (3 + 2)= 4 (4 + 2) = 5 (5 + 2) =

3 = 1.73 8 = 2.83 15= 3.87 24 = 4.90 35 = 5.92

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consider: octahedral, low spin d4 t2g4 eg N=2

consider: octahedral, high spin d4 t2g3 eg1 N=4

eff = N ( N + 2) = 2( 2 + 2) = 2.83 B. M.
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eff = N ( N + 2) = 4( 4 + 2) = 4.90 B. M.
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Blackman p 570

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Colours of Transition Metal Complexes

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Colours of Transition Metal Complexes HEXAAQUA COMPLEXES [M(H2O)6]2+

Mn(II)

Fe(III)

Co(II)

Ni(II)

Cu(II)

Zn(II)

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Blackman p 570

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Most transition metal complexes are coloured. By definition that means they absorb electromagnetic radiation somewhere in the visible region of the spectrum (400 700 nm) Light not absorbed remains to be detected by our eyes.

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Complementary colours Light not absorbed remains to be detected by our eyes i.e. the light transmitted (seen by our eyes) is complementary to the light absorbed; opposite on the colour wheel
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Sample absorbs all light except that coloured green. Green is perceived.

Sample absorbs violet, red and orange light. Blue, green and yellow light pass through. Green is perceived.

Important concept!!!!
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Blackman p 570

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This diagram will be provided in the exam. You need to understand how to use it.
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Transition metal ions and gem stones Emeralds are derived from the mineral bery which is beryllium aluminium silicate 3BeO.Al2O3.6SiO2 Some of the Al3+ ions in beryl replaced by Cr3+ and the characteristic colour of emerald results. 3BeO.(Cr2O3).Al2O3.6SiO2

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Gem Stones

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[Ti(H2O)6]3+ d1 system

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When white light shines on a filter that absorbs in the yellow-green region, the emerging light is violet. Because the complex ion [Ti(H2O)6]3+ absorbs yellow-green light, a solution of it is violet.

Important concept
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Approximate relationship of wavelength of Visible light absorbed to colour observed [CrCl2(H2O)4]+ Absorbed wavelength in nm (colour) 400 (violet) 450 (blue) 490 (blue-green) Cr2O7
2-

Observed colour

[Cu(NH3)4]2+ [Cr(H2O)6]3+

Greenish yellow Yellow Red Violet Dark blue Blue green

570 (yellow-green) 580 (yellow) Colour(s) transmitted 600 (orange) 650 (red)

CrO42Colour(s) absorbed Absorbing species

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Several octahedral complexes of Cr3+ and their colours


isomer [Cr(H2O)6]Cl3 [Cr(H2O)5Cl]Cl2 [Cr(H2O)4Cl2]Cl [Cr(NH3)6]Cl3 [Cr(NH3)5Cl]Cl2 [Cr(NH3)4Cl2]Cl Colour Violet Blue-green Green Yellow Purple violet

The ligands influence the colours of transition metal complexes.

WHY?

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See page 571 Blackman

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Absorption of light must result in some energetic change to the system (excitation). In transition metal complexes, visible light absorption excites electrons from lower energy d orbitals to higher energy d orbitals. Energy of absorbed light () for one photon is inversely proportional to the wavelength of the light.

hc E=

h = Plancks constant c = speed of light in a vacuum

Energy of light must match the d-orbital splitting energy for light to be absorbed.

hc o / t = Joules

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Blackman p 570

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d1

[Ti(H2O)6]3+

Ground state
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Excited state
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d1

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Recall that t = 4/9 o. So tetrahedral complexes must absorb at longer wavelengths than octahedral analogues (with similar ligand fields) i.e. it takes less energy to promote an electron from a lower energy d-orbital to a higher energy d-orbital.
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Blackman p 570

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A complex in an electronically excited state is very short lived (picoseconds pico =10-12) It relaxes to the ground state by releasing energy in the form of heat (molecular vibrations) - usually does not emit light.

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The magnitude of o is dependent on the ligand field strength It increases for strong field ligands. As o increases, more energy is required to promote electrons, meaning shorter wavelength.

CN- > More energy, shorter wavelength


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H2O >

FLess energy, longer wavelength


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High Energy; UV light

Lower energy

nm

CN- > phen ~ NO2- > en > NH3 ~ py > H2O > C2O42- > OH- > F- > S2- > Cl- > Br- > ICHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences

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WAVELENGTH (nm) >720 720 680 610 580 560 530 500 480 430 410 <400

COLOUR ABSORBED Infrared Red Red-orange Orange Yellow Yellow-green Green Blue-green Blue Indigo Violet ultraviolet Joules (for one photon)

COMPLEMENTARY COLOUR Colourless Green Blue-green Blue Indigo Violet Purple Red Orange Yellow Lemon-yellow Colourless

o (kJ mol1) <165 166 176 196 206 214 226 239 249 279 292 >299

hc o / t =

hcA o / t = 1000

kJ mol-1 (for one mole of photons)

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Blackman p 571

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Consider that an octahedral Cr(III) complex has an absorption band at 486 nm. Calculate the magnitude of the crystal field splitting for this complex.
19 hc (6.626 10 J s)(2.998 10 8m s-1 ) = = = 4.087 10 J 9 (486 10 m) 34

These energies are usually expressed in units of kJ mol-1 so we need to convert this

= 4.087 10

19

J 6.02 10 mol
23

1 kJ 1 = 246.1 kJ mol 1000 J

Avogadro constant
Divide the number in Joules by 1000 to convert to kJ.
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HEXAAQUA COMPLEXES [M(H2O)6]2+

Mn(II)

Fe(III)

Co(II)

Ni(II)

Cu(II)

Zn(II)

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Blackman p 572

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Zn(II)

Colourless Why?
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Zn(II) is d10

d10

The eg orbitals are already full there is no space to fit a promoted electron.

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Blackman p 572

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Mn(II)

Very, very pale pink. Why?

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d5
This configuration cant occur!

X
High spin, d5
This excited state cant exist cant have two electrons with all 4 quantum numbers the same called spin forbidden.
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Equilibrium

p. 561 Blackman

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Many reactions of transition metal complexes are reversible that is they are equilibrium reactions and the position of the equilibrium can be altered by changes in the concentration of reactants or products, or other factors like temperature.

The Portuguese weather rooster changes colour with the weather. Portions are coated in cobalt chloride, which respond to changes in humidity. In dry weather, it is blue, due to formation of [CoCl4]2-. In humid conditions, pink trans-[CoCl2(H2O)4] is formed.

[CoCl4]2- + 4H2O(l)
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trans-[CoCl2(H2O)4] + 2Cl-(aq)
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Blackman p 561

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Le Chateliers Principle: If an outside influence upsets an equilibrium, the system undergoes a change in a direction that counteracts the disturbing influence and, if possible, returns the system to equilibrium. (p. 364 Blackman)

[CoCl4]2- + 4H2O(l)

trans-[CoCl2(H2O)4] + 2Cl-(aq)

blue
If water is removed or Cl- ions added, the equilibrium will move to the left, favouring formation of blue [CoCl4]2-.

pink
If water is added or Cl- ions removed, the equilibrium will move to the right, favouring formation of pink trans-[CoCl2(H2O)4]2-.

CHEM1010 Transition Metal Chemistry

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Blackman p 547

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Equilibrium Constant For the general reaction The equilibrium constant K for the reaction is given by

[C] [D] K= a b [A] [B]

If K is large, the equilibrium lies to the right (products); If K is small, the equilibrium lies to the left (reactants). Different names, formation constant, equilibrium constant, association constant, binding constant all meaning the same thing
CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences

Blackman p 547

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The stability of a complex in solution refers to the degree of association between the two species involved in the state of equilibrium [Ni(H2O)6]2+ + 6NH3 [Ni(NH3)6]2+ + 6H2O The magnitude of the stability (or formation constant) for the association quantitatively expresses the stability

[Ni(NH3)62 + ] K= [Ni(H2O)62 + ][NH3]6


K is an equilibrium constant
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[M(H2O)6]2+ + 6NH3

[M(NH3)6]2+ + 6H2O

[Ni(H2O)6]2+
CHEM1010 Transition Metal Chemistry

[Ni(NH3)6]2+
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Blackman p 561

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separate steps - stepwise reactions [Ni(H2O)6]2+ + NH3 [Ni(OH2)5(NH3)]2+ + NH3 [Ni(OH2)4(NH3)2]2+ + NH3 [Ni(OH2)3(NH3)3]2+ + NH3 [Ni(OH2)2(NH3)4]2+ + NH3 [Ni(OH2) (NH3)5]2+ + NH3 [Ni(OH2)5(NH3)]2+ + H2O [Ni(OH2)4(NH3)2]2+ + H2O [Ni(OH2)3(NH3)3]2+ + H2O [Ni(OH2)2(NH3)4]2+ + H2O [Ni(OH2)(NH3)5]2+ + H2O [Ni(NH3)6]2+ + H2O

CHEM1010 Transition Metal Chemistry

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Blackman p 561

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overall we can write:[Ni(H2O)6]2+ + xNH3 [Ni(OH2)6-x(NH3)x]2+ + H2O


2+

[Ni(H2O)6 x (NH3)x ] x = [Ni(H2O)62 + ][NH3]x


- Cumulative formation constants e.g. [Ni(H2O)6]2+ + 3NH3 [Ni(OH2)3(NH3)3]2+ + H2O

[Ni(H2O)3(NH3)32 + ] 3= [Ni(H2O)62 + ][NH3]3


CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences

Blackman p 561-562

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3 = K1 x K2 x K3
and, in general

k = K1 x K2 x K3 x . . . . x Kk

Important concept

The magnitude of n for a complex is a measure of how far the formation reaction for that complex proceeds towards completion. If n is small the complex shows little tendency to form; if n is large the complex forms almost completely.

CHEM1010 Transition Metal Chemistry

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Blackman p. 562 Ligand NH3 Metal Co(II) Ni(II) en Co(II) Ni(II) Equilibrium Co2+(aq) + 6NH3(aq) Ni2+(aq) + 6NH3(aq) Co2+(aq) + 3en(aq) Ni2+(aq) + 3en(aq) [Co(NH3)6]2+(aq) [Ni(NH3)6]2+(aq) [Co(en)3]2+(aq) [Ni(en)3]2+(aq) n 6 6 3 3

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n 5.0 104 2.0 108 1.0 1014 4.1 1017

Conclusion 1: Identity of the metal affects stability. Here, Ni2+ complexes of the same ligand are more stable than Co(II) complexes. Cu(II) complexes are generally the most stable of the first row divalent (2+) transition metal ions, when comparing complexes with the same ligands.
(CHEM2050 Irving Williams series
CHEM1010 Transition Metal Chemistry

Mn(II) < Fe(II) < Co(II) < Ni(II) < Cu(II) > Zn(II) )
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Blackman p 562

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Conclusion 2: Ligands can show different affinities for various oxidation states of the same metal ion.
Ligand NH3 Metal Co(II) Co(III) en Co(II) Co(III) Equilibrium Co2+(aq) + 6NH3(aq) Co3+(aq) + 6NH3(aq) Co2+(aq) + 3en(aq) Co3+(aq) + 3en(aq) [Co(NH3)6]2+(aq) [Co(NH3)6]3+(aq) [Co(en)3]2+(aq) [Co(en)3]3+(aq) n 6 6 3 3 n 5.0 104 4.6 1033 1.0 1014 5.0 1048

Cobalt(III) is favoured in each case.

CHEM1010 Transition Metal Chemistry

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Blackman p 563

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Compare the numbers for complexes of monodentate (NH3), bidentate (en) and hexadentate (EDTA) ligands:
Ligand NH3 en edta Metal Ni(II) Ni(II) Ni(II) Equilibrium Ni2+(aq) + 6NH3(aq) Ni2+(aq) + 3en(aq) Ni2+(aq)+EDTA4 (aq) [Ni(NH3)6]2+(aq) [Ni(en)3]2+(aq) [Ni(EDTA)]2(aq) n 6 3 1 n 2.0 108 4.1 1017 3.6 1018

The bidentate ligand en results in a more stable complex (larger n) than the monodentate ligand NH3. The hexadentate edta ligand results in the most stable complex (largest n), compared to the en and NH3 complexes. Conclusion 3: The number of chelate rings formed affects the stability of the complex. More chelate rings = more stable.
CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences

Blackman p 563

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Important concept
Complexes containing chelate rings are usually more stable than similar complexes without chelate rings. Generally, as the number of chelate rings increases, so does the stability. termed - THE CHELATE EFFECT

CHEM1010 Transition Metal Chemistry

School of Chemistry and Molecular Biosciences

Blackman p 563

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Compare: A monodentate system [Ni(NH3)6]2+(aq) + H2O(l) With a chelate [Ni(NH3)5(OH2)]2+ + NH3(aq)

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Ligand EDTA EDTA

Metal Co(II) Co(III)

Equilibrium Co2+(aq)+EDTA4 (aq) Co3+(aq)+EDTA4 (aq) [Co(EDTA)]2(aq) [Co(EDTA)](aq)

n 1 1

n 2.8 1016 2.5 1041

For EDTA4 we see the effect of both the charge on the metal ion and the chelate effect.

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NOTE: The value of n DOESNT tell us anything about rate of reaction! [Co(NH3)6]3+ + 6H3O+ [Co(OH2)6]3+ + 6NH4+

The stability constant for this reaction is 1025, so at equilibrium [Co(OH2)6]3+ will be strongly favoured in acidic solution. However, [Co(NH3)6]3+ is stable in 1 M acid for several days. It is kinetically inert to ligand substitution. Cr(III) and low spin Co(III) octahedral complexes are kinetically inert and undergo ligand exchange reactions slowly. (Why inert? Neither have electrons in the eg orbitals, and the t2g orbitals are half or completely filled).
CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences