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THE UNIVERSITY OF QUEENSLAND

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CHEM1010 Transition Metal Chemistry

School of Chemistry and Molecular Biosciences

THE UNIVERSITY OF QUEENSLAND
AUSTRALIA

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

PHONE 3365 3900 Room 205 Chemistry

CHEM1010 Transition Metal Chemistry

School of Chemistry and Molecular Biosciences

THE UNIVERSITY OF QUEENSLAND
AUSTRALIA

Associate Lecturer at UQ since 2010. I’m 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.

CHEM1010 Transition Metal Chemistry

School of Chemistry and Molecular Biosciences

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”. These notes are incomplete and require you to add material. 2nd Edition. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . Note: First edition cannot be used for inorganic nomenclature section.THE UNIVERSITY OF QUEENSLAND AUSTRALIA Figures in these lectures notes are taken from Blackman.

THE UNIVERSITY OF QUEENSLAND AUSTRALIA CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

THE UNIVERSITY OF QUEENSLAND AUSTRALIA CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

THE UNIVERSITY OF QUEENSLAND AUSTRALIA Why is this stuff (transition metal chemistry) important? Note: This first section on why transition metals are important is not examinable. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .THE UNIVERSITY OF QUEENSLAND AUSTRALIA 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.

llnl.gov/nif/library/aboutlasers/how.http://www.html THE UNIVERSITY OF QUEENSLAND AUSTRALIA Chromium is responsible for the lasing behavior of the crystal. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . Chromium atoms absorb green and blue light and emit or reflect only red light.

Metal Ions in Biology THE UNIVERSITY OF QUEENSLAND AUSTRALIA Worldwide prevalence of anaemia 1993-2005. WHO Global Database on Anaemia CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

No specific role known in humans. glutamine synthetase. e. sulfite oxidase. Component of redox enzymes e. Needed for several enzymes. hydrogenase (bacteria) Found in several enzymes. Mn superoxide dismutase.THE UNIVERSITY OF QUEENSLAND Essential Transition Metals Vanadium Manganese Biological Function AUSTRALIA Essential for rats and chickens. other enzymes Vitamin B12 Urease (plants).g. Cu-Zn superoxide dismutase detoxifies free radicals. Hemoglobin. myoglobin. Bound to insulin. School of Chemistry and Molecular Biosciences Iron Cobalt Nickel Copper Zinc Molybdenum (only essential 2nd row transition metal) CHEM1010 Transition Metal Chemistry .g. around 10% of all proteins contain Zn.

energy pathways and many other functions. drug metabolism. Other iron proteins – involved in DNA synthesis. 65% of the iron present in a human.a tetrameric protein O2 uptake in the lungs and transport in the blood stream. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .THE UNIVERSITY OF QUEENSLAND AUSTRALIA hemoglobin (Hb) .

THE UNIVERSITY OF QUEENSLAND AUSTRALIA The organic core of hemoglobin Porphyrin Heme (Porphyrin + iron) School of Chemistry and Molecular Biosciences CHEM1010 Transition Metal Chemistry .

chemistry.THE UNIVERSITY OF QUEENSLAND AUSTRALIA http://www.wustl.edu/~edu dev/LabTutorials/Hemoglobin/chang emovie.html A heme site in hemoglobin CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

The reaction is carried out under conditions of 250 atm.THE UNIVERSITY OF QUEENSLAND AUSTRALIA DINITROGEN . N2 and H2 gases are reacted over an Fe3+ catalyst in which Al2O3 and K2O are used as promoters. mostly in the form of anhydrous ammonia. 1% of the world's annual energy supply is consumed in the Haber process. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . 450-500 °C. N2 + 10H+ + 8e.thermodynamically stable. That fertilizer is responsible for sustaining 50% of the Earth's population. ammonium nitrate and urea.4 kJ mol-1 The Haber process produces 100 million tons of nitrogen fertilizer per year. resulting in a yield of 10-20%: N2(g) + 3H2(g) → 2NH3(g) ΔHθ = -92. so reduction requires a large amount of energy.→ 2NH4+ + H2 In the Haber Process.

THE UNIVERSITY OF QUEENSLAND How Nature does it:- AUSTRALIA Rhizobium bacteria. which live in legume root nodules contain nitrogenase protein. MoFe7S8 CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

et al. 974 (2011) DOI: 10. Science 337. Wiig. C. Lancaster. 1672 (2012). 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. Hu. C. M.THE UNIVERSITY OF QUEENSLAND AUSTRALIA Science 334. W.1206445 Kyle M. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . A. Ribbe. Y. Lee.1126/science. J.

.THE UNIVERSITY OF QUEENSLAND AUSTRALIA Metal ions in Medicine • cis-[Pt(NH3)2Cl2] – cisplatin. Pt. an anticancer drug • Radionucleotides – 64Cu for tumour imaging • Antiarthritic drugs – gold complexes Metal ions in Industry • Catalysts e. Pd). . CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .g.Optically active metal complexes as agents for synthesis of chiral pharmaceuticals.catalytic converters in cars for removal of nitrogen oxides from exhaust (Rh.

THE UNIVERSITY OF QUEENSLAND AUSTRALIA We are at a wonderful time for chemistry. or biology in the 1950s. It is. 2007. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . just before quantum mechanics made the world impossibly strange. I believe. just before the double helix obliterated the old biology. George M. Whitesides Priestley Medal Address. in the position of physics in the 1910s.

THE UNIVERSITY OF QUEENSLAND AUSTRALIA CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

THE UNIVERSITY OF QUEENSLAND AUSTRALIA CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

Blackman p 138. 546 THE UNIVERSITY OF QUEENSLAND AUSTRALIA The Aufbau Principle – allows us to write electron configurations CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

n is the principal quantum number) e. 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. electron configuration [Ar]4s23d3.g. http://goldbook. Cd. 4d.org/T06456. group number of 5.g. 3d. but we can think of them as honorary transition metals because of their similar chemistry.html Zn. Vanadium. or which can give rise to cations with an incomplete d sub-shell".Blackman p 545-546 THE UNIVERSITY OF QUEENSLAND AUSTRALIA • • Transition metal atoms:characterised by d valence orbitals (e.iupac. Hg (Group 2B elements) are d-block metals. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . IUPAC definition: A transition metal is "an element whose atom has an incomplete d sub-shell.

Two orbitals lie on axes. three orbitals lie between axes.THE UNIVERSITY OF QUEENSLAND AUSTRALIA The five 3d orbitals means a maximum of 10 d electrons. It is all about the d-orbitals & d-electrons!!! CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

THE UNIVERSITY OF QUEENSLAND AUSTRALIA CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

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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.

CHEM1010 Transition Metal Chemistry

School of Chemistry and Molecular Biosciences

THE UNIVERSITY OF QUEENSLAND
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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 don’t 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

CHEM1010 Transition Metal Chemistry

School of Chemistry and Molecular Biosciences

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!!!

CHEM1010 Transition Metal Chemistry

School of Chemistry and Molecular Biosciences

p. •Elements in the middle have the greatest number of possible oxidation states. •For the same element. 546 Blackman 2nd ed. p. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . THE UNIVERSITY OF QUEENSLAND AUSTRALIA = common oxidation states Table 13.1. • For ions in the same oxidation state. the number of d electrons decreases as oxidation state increases. the number of d electrons increases going across the row from left to right. 546 Blackman 2nd ed.

The number of d electrons.THE UNIVERSITY OF QUEENSLAND AUSTRALIA The higher oxidation states are limited by:• • • The effective nuclear charge – it becomes energetically unfavourable to remove more electrons. 2Mn3+ → Mn2+ + Mn4+ Low oxidation states are unstable due to spontaneous oxidation by air. The intermediate oxidation states are often unstable due to disproportionation reactions leading to more stable reduced and oxidized forms. 2Cr2+ + O2 + 2H+ → 2Cr3+ + H2O2 • CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

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) School of Chemistry and Molecular Biosciences CHEM1010 Transition Metal Chemistry .THE UNIVERSITY OF QUEENSLAND AUSTRALIA 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.

THE UNIVERSITY OF QUEENSLAND AUSTRALIA 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 CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

) CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . before the 3d electrons are lost. 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. (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 UNIVERSITY OF QUEENSLAND AUSTRALIA 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. the one 4s electron will be lost and one 3d electron.

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 year’s exam required knowledge of the number of d-electrons.THE UNIVERSITY OF QUEENSLAND AUSTRALIA Alternative method: Number of d-electrons = Number of electrons in ion – number electrons in last noble gas element. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . Ni2+ : Ni Z=28.

d1 d2 d3 d4 d5 d6 d7 d8 d9 d10 CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .THE UNIVERSITY OF QUEENSLAND AUSTRALIA Divalent first row metal ions Atomic Number 21 22 23 24 25 26 27 28 29 30 Element Sc Ti V Cr Mn Fe Co Ni Cu Zn Ionic Charge 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ d electron Config.

THE UNIVERSITY OF QUEENSLAND AUSTRALIA 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. Ar (Z=18) was the last noble gas. Alternately. so number of d electrons = 24 -18 = 6 d electrons. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . Co (Z=27). so Co3+ has 27 .3 = 24 electrons. so Co3+ will have 6 d electrons.

C.THE UNIVERSITY OF QUEENSLAND AUSTRALIA Which two commonly occurring first-row transition metal ions have FIVE 3d electrons? A. p 546 CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . B. E. Co3+ and Ni2+ Fe2+ and Co3+ V5+ and Cr6+ Mn2+ and Fe3+ Co4+ and Ni5+ Blackman worked example 13. D.1.

THE UNIVERSITY OF QUEENSLAND AUSTRALIA CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

The Lewis bases that are bonded to the metal ion in this way are called ligands. Lewis bases donate electron pairs. The Lewis base donates an electron pair to the metal ion.THE UNIVERSITY OF QUEENSLAND AUSTRALIA Coordination Chemistry d-block metal ions are Lewis acids and they form compounds with Lewis bases. ([From Latin ligandus. Lewis acids (e.g. d-block metal ions) accept electron pairs. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . to bind) The compound formed by a metal ions and its ligands is called a complex.

Lewis acid: electron pair acceptor – the metal ion.Blackman p 552 THE UNIVERSITY OF QUEENSLAND AUSTRALIA 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. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . Lewis base: electron pair donor – the ligand.

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. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .THE UNIVERSITY OF QUEENSLAND AUSTRALIA Consider BF3 (B not a transition metal.

This is a coordinate covalent bond N Lone Pair B N B empty orbital Coordinate bonds are normal two electron bonds.THE UNIVERSITY OF QUEENSLAND AUSTRALIA H H N H F B F F H F H N B F H F Both electrons in the B-N bond are contributed by N. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

Ligand Metal ion School of Chemistry and Molecular Biosciences . NH3 can use the lone pair of electrons on the N to coordinate.LIGANDS Complex or complex ion THE UNIVERSITY OF QUEENSLAND AUSTRALIA Any atom within a molecule or ion bearing a lone pair of electrons can potentially coordinate to a metal ion. CHEM1010 Transition Metal Chemistry The coordinated atom is known as the donor atom.

CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .Blackman p 547-551 THE UNIVERSITY OF QUEENSLAND AUSTRALIA •A metal ion can have several donor atoms coordinated at the same time.

I-. Octahedron An octahedral ligand arrangement School of Chemistry and Molecular Biosciences CHEM1010 Transition Metal Chemistry .Blackman p 547-551 THE UNIVERSITY OF QUEENSLAND AUSTRALIA LIGANDS Dentate = having teeth A monodentate ligand – NH3 Other common monodentate ligands are F-. Br-. H2O. Cl-.

THE UNIVERSITY OF QUEENSLAND AUSTRALIA Denticity The number of donor groups from a given ligand attached to the same central atom. e.g. 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. “teeth” CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

4-dionato or or acetylacetonato “ethylenediamine” or “acac” 5-membered chelate ring CHEM1010 Transition Metal Chemistry 6-membered chelate ring School of Chemistry and Molecular Biosciences . meaning claw) Ring A bidentate ligand – A bidentate ligand – 1.Blackman p 547-551 THE UNIVERSITY OF QUEENSLAND AUSTRALIA Chelate (Chelation (from Ancient Greek χηλή. chelè.2-diaminoethane pentane-2.

2-diaminoethane CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .Blackman p 553 THE UNIVERSITY OF QUEENSLAND AUSTRALIA monodentate chelate (bidentate) compare en = 1.

3diamine 2.7-triazaheptane [Co(acac)3] K3[Cr(ox)3] [Co(dien)2]3+ ox2dien CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .4.THE UNIVERSITY OF QUEENSLAND AUSTRALIA Name of ion or molecule ethylenediamine Propane-1.2-diaminoethane (ethylenediamine) Propane-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-2.4.4-dionato acac oxalato 1.10phenanthroline Pentane-2.4dionate ion oxalate 1.2’-bipyridine 1.2’-bipyridine 1.3diamine 2.7triazaheptane Formula Name of coordinated ligand 1.

p.THE UNIVERSITY OF QUEENSLAND AUSTRALIA Ethylenediaminetetraacetic acid a polydentate ligand .EDTA [Co(EDTA)]CHEM1010 Transition Metal Chemistry Fig 13. 548 Blackman School of Chemistry and Molecular Biosciences .6.

Blackman p 549-550 THE UNIVERSITY OF QUEENSLAND AUSTRALIA Multidentate ligands can have the same or mixed donor atoms (e.g. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . 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 (µ -OOCCH3)4] Figure 13.7, Blackman 2nd ed.

CHEM1010 Transition Metal Chemistry

School of Chemistry and Molecular Biosciences

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”.

CHEM1010 Transition Metal Chemistry

School of Chemistry and Molecular Biosciences

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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
CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences

Quiz 3 available now! CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . podium Friday May 24 from 10-12 Transition metal drop-in Friday May 24 from 2:10-4.THE UNIVERSITY OF QUEENSLAND AUSTRALIA Dr Vamvounis – consultation “drop-in” session on organic chemistry.

Blackman p 554 THE UNIVERSITY OF QUEENSLAND AUSTRALIA 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. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

CHEM1010 Transition Metal Chemistry Ligand Coordination number = 6. as there are 6 N atoms coordinated.THE UNIVERSITY OF QUEENSLAND AUSTRALIA [Co(NH3)6]3+ Metal ion Ionic charge Note: There will be a counterion or ions balancing any charge but outside the complex ion. School of Chemistry and Molecular Biosciences . Complex or complex ion Coordination number = count the number of donor atoms attached to the metal ion. This is indicated by them being written outside the square brackets.

CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . a monoanion) • The overall charges must cancel: x + 3 x -1 = 0. so must be Co(III) = Co3+.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-.THE UNIVERSITY OF QUEENSLAND AUSTRALIA http://en.wikipedia.

Composition: central metal ion+ligands+counter ion/s (if needed) Called a complex ion if charged. [Cu(NH3)4]SO4 counterion (outside the Central ligands metal (inside the square brackets) ion square brackets) CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . Lewis acid-base adducts.g. Coloured. often with unusual magnetic properties e.THE UNIVERSITY OF QUEENSLAND Summary of Metal Complexes: AUSTRALIA Contain coordinate covalent bonds.

5NH3 CoCl3. some more slowly. add AgNO3.nNH3 with n = 4.6NH3 CoCl3.THE UNIVERSITY OF QUEENSLAND AUSTRALIA Consider CoCl3. Some Cl– precipitates as AgCl immediately. this difference indicates the number of Cl– which are ionic (fast) and covalent (slow) CoCl3.4NH3 CoCl3. 5 or 6 4 different compounds are possible. How can we have these compounds with various compositions? Dissolve in water.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 CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . [Au(CN)2]− . and [ReH9]2− . especially those of the 3+ lanthanide cations. formed when AgCl dissolves in ammonia solution.quite rare. these complexes are found in instances in which ligands are large and steric repulsions are dominant. and 9: various Further types of coordination geometry exist for large cations. formed during the extraction of gold from its ore. for example. Coordination number 3: trigonal planar . 553 Coordination Geometries Coordination number 2: collinear. [Mo(CN)8]4− .THE UNIVERSITY OF QUEENSLAND AUSTRALIA Blackman p. [Pt{P(phenyl)3 }3]. Coordination numbers 7. Collinear complexes . for example. [NbF7] 2− . and [Ag(NH3)2]+ . 8. [La(edta)(H2O)3]-.common in the case of heavy metal cations of d10 electron configuration.

also common for Ni(II). 554 d10 metal ion should be Cu(I) not Cu(III). Pt(II). such as Co2+ . Cu(III) is d8. and d7 species. Note: Mistake p. There is more space to fit ligands around a tetrahedral metal centre. and [CoCl2(4–methylpyridine)2]. Examples: [ZnCl2(pyridine)2]. Ir(I). so it is especially favoured for small metal ions with bulky ligands.common for d10 metal ion species such as Zn2+ and Ga3+ . CHEM1010 Transition Metal Chemistry THE UNIVERSITY OF QUEENSLAND AUSTRALIA School of Chemistry and Molecular Biosciences .Coordination number 4: tetrahedral . Square planar – [Cu(NH3)4]2+ . as the ligands in a square planar complex will be closer together. Rh(I) d8 systems. [GaCl4]− .

Examples: square-pyramidal complexes:[Ni(CN)5]3− and [Cu(hfacac)2(OH2)] . [Fe(CO)3(PF3)2]. and [Mn(CO)4NO]. Examples: trigonal-bipyramidal complexes:[CuCl5]3−.common in the case of complexes of metal ions of coordination number 5. (hfacac = hexafluoroacetylacetonate) CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .Blackman p. 554 THE UNIVERSITY OF QUEENSLAND AUSTRALIA Coordination number 5: trigonal-bipyramidal and squarepyramidal .

THE UNIVERSITY OF QUEENSLAND AUSTRALIA Coordination number 6: Octahedral Donor atoms at either (approximately) 90° (cis) or 180° (trans) to each other. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

THE UNIVERSITY OF QUEENSLAND AUSTRALIA Coordination compounds may exhibit isomerism. (Do you remember this from the early organic chemistry lectures?) CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . just like organic compounds (only better).

same molecular formula) Linkage isomers (different atoms in the same ligand bound to the metal ion) THE UNIVERSITY OF QUEENSLAND AUSTRALIA 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 CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .Isomerism in Coordination Compounds Isomers (same formula. different properties) Structural isomers (different bonds.

• Physical properties are completely different.Blackman p 555-558 THE UNIVERSITY OF QUEENSLAND AUSTRALIA Ionisation isomers • Interchange of counter ions and ligands. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

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]Cl2·H2O blue-green green [Cr(OH2)4Cl2]Cl·2H2O CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .Blackman p 555-558 THE UNIVERSITY OF QUEENSLAND AUSTRALIA Hydrate isomers Results from the different numbers of water molecules that can be coordinated to a metal ion.

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] CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .Blackman p 555-558 THE UNIVERSITY OF QUEENSLAND AUSTRALIA Coordination isomers .

Blackman p 555-558 Linkage isomers (which atom in a ligand is bound to the metal ion) THE UNIVERSITY OF QUEENSLAND AUSTRALIA Requires two potential donors on the one ligand: e. CN-. These ligands are called ambidentate.g. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . as they have more than one potential donor atom. NO2-. SCN-.

Geometric isomers cis and trans cis-[Co(NH3)4Cl2]+ Two ligands at 90° CHEM1010 Transition Metal Chemistry trans-[Co(NH3)4Cl2]+ Two ligands at 180° School of Chemistry and Molecular Biosciences . but a different orientation of their atoms in space. different arrangements) Stereoisomers – isomers with the same order of attachment of atoms.Blackman p 555-558 THE UNIVERSITY OF QUEENSLAND AUSTRALIA Stereoisomers (same bonds.

lung. gullet. stomach and ovarian cancers. Trans isomer is inactive. bladder. It is most commonly used to treat testicular. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .Blackman p 555-558 THE UNIVERSITY OF QUEENSLAND Geometric Isomerism AUSTRALIA cis-[Pt(NH3)2Cl2] trans-[Pt(NH3)2Cl2] Cisplatin is a chemotherapy drug that is given as a treatment for some types of cancer.

All three NH3 ligands are: . This is the facial isomer. Facial (fac) CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .Blackman p 557 THE UNIVERSITY OF QUEENSLAND AUSTRALIA Geometric isomers fac and mer Look at the set of three ammine (NH3) ligands.cis (90°) to each other.on the same face of the octahedron. .

plingfactory.. html School of Chemistry and Molecular Biosciences .THE UNIVERSITY OF QUEENSLAND AUSTRALIA Look at the set of three ammine (NH3) ligands. One NH3 ligand is cis to the two others. . .Two of the NH3 ligands are trans (180°) to each other.All three NH3 ligands are coplanar with the metal ion and each other.de/Science/Atlas/Kennkart en%20Algen/Diatomeen/Source/Meridion%20sp. Meridion species of diatom (algae) Meridional (mer) CHEM1010 Transition Metal Chemistry http://www.

THE UNIVERSITY OF QUEENSLAND AUSTRALIA fac-[Co(NH3)3Cl3] mer-[Co(NH3)3Cl3] CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

one ligand cis to the two others.THE UNIVERSITY OF QUEENSLAND AUSTRALIA Facial isomer – 3 ligands all cis to each other. Meridional isomer – 2 ligands trans to each other. School of Chemistry and Molecular Biosciences CHEM1010 Transition Metal Chemistry .

but a different orientation of their atoms in space. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . Optical isomers Enantiomers – stereoisomers that are nonsuperimposable mirror images of each other.10. p.THE UNIVERSITY OF QUEENSLAND AUSTRALIA Stereoisomerism Stereoisomers – isomers with the same order of attachment of atoms. Figure 17. 749 Blackman 2nd ed.

THE UNIVERSITY OF QUEENSLAND AUSTRALIA CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

THE UNIVERSITY OF QUEENSLAND AUSTRALIA Are these isomers of each other? [Co(ox)3]3- CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

enantiomers Are they mirror images? Yes!! CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .THE UNIVERSITY OF QUEENSLAND AUSTRALIA Optical isomers .

they are isomers. as they are non-superimposable mirror images.THE UNIVERSITY OF QUEENSLAND AUSTRALIA Are they superimposable? No!! ∴They are enantiomers. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . If you have to break bonds to make them identical. If you can rotate two structures so that they are identical then they are not isomers.

Can this complex ion exist as optical isomers? Yes it can These are mirror images which cannot be superimposed.THE UNIVERSITY OF QUEENSLAND AUSTRALIA Consider the following complex ion. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

Cis and trans isomers not possible CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . Cis and trans isomers possible 2.THE UNIVERSITY OF QUEENSLAND AUSTRALIA Consider the following complex ion: are cis and trans isomers possible? 1.

THE UNIVERSITY OF QUEENSLAND AUSTRALIA cis (two optical isomers) trans No optical isomers CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

Yes it can exist as optical isomers 2. No it cannot exist as optical isomers CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .THE UNIVERSITY OF QUEENSLAND AUSTRALIA Can the following molecule exist in enantiomeric forms? 1.

THE UNIVERSITY OF QUEENSLAND AUSTRALIA Non-superimposable mirror images – therefore they are optical isomers (enantiomers). CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

Blackman p 558-560 2nd edition only THE UNIVERSITY OF QUEENSLAND AUSTRALIA RULES FOR NAMING METAL COMPLEXES Look on the Blackboard page!!!! (i) Cations are named before anions.g. (ii) The names of anionic ligands always end in the suffix “-o”. Ligands with names ending in ide. ito and ato. This is the same rule that applies to other ionic compounds e.g. ite or ate have this suffix changed to ido. e. a chloride ion when bound to a metal is a chlorido ligand. with a space between the ions. respectively. a carbonate ion when bound to a metal is a carbonato ligand CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . sodium chloride.

tri = 3. tetrakis = 4.g. enclose the ligand name in brackets and use the following prefixes instead bis = 2. 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.2-diaminoethane)copper(II) chloride. [Cu(en)2]Cl2 is bis(1. penta = 5.2-diaminoethane)copper(II) chloride NOT di(1.2-diaminoethane). hexa = 6.g. their number is specified by the prefixes di = 2. tetra = 4.g. 1. If the name of the ligand already incorporates one of these prefixes (e.THE UNIVERSITY OF QUEENSLAND AUSTRALIA (iii) A neutral ligand is given the same name as the neutral molecule e. tris = 3. e. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

the ligands are named first.g. cis-[Pt(NH3)2ClBr] cis-diamminebromidochloridoplatinum(II) A B C CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . in alphabetical order without regard to charge. Ignore the prefix in front if any. e. followed by the name of the metal.THE UNIVERSITY OF QUEENSLAND AUSTRALIA (v) In the name of the complex.

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). 560 Blackman [CoCl2(NH3)4].tetraamminedichloridocobaltate(III) ion CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .THE UNIVERSITY OF QUEENSLAND AUSTRALIA (vi) Negative (anionic) complex ions always end in the suffix –ate. 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.

THE UNIVERSITY OF QUEENSLAND AUSTRALIA (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) CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

Blackman p 559 Name of ion or molecule Formula Name of coordinated ligand THE UNIVERSITY OF QUEENSLAND AUSTRALIA 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 CHEM1010 Transition Metal Chemistry .

tri. penta.(bis-).(pentakis-).(tris-). the ligand already has a multiple prefix (di-) in its name di.2-diaminoethane)nickel(II) bromide the prefix is tris (NOT tri). hexa.(tetrakis-).(hexakis-) CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . tetra.THE UNIVERSITY OF QUEENSLAND AUSTRALIA 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.

THE UNIVERSITY OF QUEENSLAND AUSTRALIA 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) CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

THE UNIVERSITY OF QUEENSLAND AUSTRALIA Why are metal complexes coloured???????? CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

enabling the concentration of aspartame in a sweetener sachet to be determined.THE UNIVERSITY OF QUEENSLAND AUSTRALIA 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. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

halogen). S. P. The ligand donor atom (the Lewis base) typically has a high electronegativity (N. The partial negative charge results in an electrostatic attraction to the positively charged metal ion. δH δ+ N H δ+ δ+ H CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .Blackman p 565-570 THE UNIVERSITY OF QUEENSLAND AUSTRALIA Crystal Field Model A simple approximation – treats the coordinate bonds as electrostatic in origin. O.

Blackman p 566 THE UNIVERSITY OF QUEENSLAND AUSTRALIA The five 3d-orbitals Two point along the axes dz2 dx2-y2 Three point between the axes dxy dxz dyz CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

Blackman p 567 THE UNIVERSITY OF QUEENSLAND AUSTRALIA CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

THE UNIVERSITY OF QUEENSLAND AUSTRALIA 1. dx2-y2 dz2 eg set – higher energy dxy dyz dxz In an octahedral complex . School of Chemistry and Molecular Biosciences CHEM1010 Transition Metal Chemistry . . 3. t2g set – lower energy The degree and nature of the energy splitting depends on the coordination geometry and the type of ligands. 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. . 2.

the energies are essentially unchanged 2 eg orbitals 3 t2g orbitals ∆o CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .Blackman p 567 THE UNIVERSITY OF QUEENSLAND AUSTRALIA d-orbital splitting – Octahedral complexes dz2 and dx2-y2 orbitals point towards the ligands (larger repulsion) so the energies are raised considerably dxy. dyz orbitals point between the ligands. dxz.

Blackman p 569 THE UNIVERSITY OF QUEENSLAND AUSTRALIA Tetrahedral complexes dz2 and dx2-y2 orbitals point between the ligands (energies are virtually unaffected) dxy. their energies are raised. dyz orbitals point towards the ligands. dxz. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . This is the reverse of what occurs for octahedral complexes.

THE UNIVERSITY OF QUEENSLAND AUSTRALIA http://www.edu/tiger/ diagrams/comp lexions CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .dlt.n cssm.

Blackman p 569 THE UNIVERSITY OF QUEENSLAND AUSTRALIA Tetrahedral complexes 3 t2 orbitals 2 e orbitals Tetrahedral ∆t CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

THE UNIVERSITY OF QUEENSLAND AUSTRALIA eg ∆o e t2 t2g ∆t Octahedral CHEM1010 Transition Metal Chemistry Tetrahedral School of Chemistry and Molecular Biosciences Important that you understand and can use these diagrams!!!! .

Blackman p 568 Electronic Configurations THE UNIVERSITY OF QUEENSLAND AUSTRALIA The most stable (ground state) d-orbital electronic configuration is a compromise between i. with orbitals filled from lowest to highest energy. minimising d electron–d electron repulsion. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . Occupying the lowest energy orbitals AND ii. opposite spins). Assuming d-orbital splitting is small (weak field case) the electronic configuration is governed by Hund’s rule (maximum number of unpaired spins). The Pauli exclusion principle is still obeyed (maximum of 2 electrons per orbital.

THE UNIVERSITY OF QUEENSLAND AUSTRALIA d1 d2 Octahedral CHEM1010 Transition Metal Chemistry Tetrahedral School of Chemistry and Molecular Biosciences .

THE UNIVERSITY OF QUEENSLAND AUSTRALIA d3 Octahedral CHEM1010 Transition Metal Chemistry Tetrahedral School of Chemistry and Molecular Biosciences .

Tetrahedral d4 d5 THE UNIVERSITY OF QUEENSLAND AUSTRALIA d6 d7 CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

Tetrahedral d8 d9 THE UNIVERSITY OF QUEENSLAND AUSTRALIA d10 CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

d2. . .d7 there are two possibilities. depending on ∆o size.Blackman p 568 Back to octahedral complexes . d3) orbitals fill But for d4 . . CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . THE UNIVERSITY OF QUEENSLAND AUSTRALIA No ambiguity in the way these (d1.

• If P>Δo then the energetically favourable electron configuration is that in which the 4th electron occupies an eg orbital (called a high spin configuration) • If P<Δo the complex adopts a low spin configuration.Blackman p 568 THE UNIVERSITY OF QUEENSLAND AUSTRALIA 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 Δo determines which electron configuration is favoured. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . that is paired with another electron in the t2g orbital.

Blackman p 568 THE UNIVERSITY OF QUEENSLAND AUSTRALIA high spin CHEM1010 Transition Metal Chemistry low spin School of Chemistry and Molecular Biosciences .

THE UNIVERSITY OF QUEENSLAND
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high spin

d5

low spin

d6

CHEM1010 Transition Metal Chemistry

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THE UNIVERSITY OF QUEENSLAND
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high spin

d7

low spin

d8

?
CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences

THE UNIVERSITY OF QUEENSLAND
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d8

d9

d10

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> OH.> Cl.> en > NH3 ~ py > H2O > C2O42.> S2.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.> F.Blackman p 572 THE UNIVERSITY OF QUEENSLAND AUSTRALIA Spectrochemical series – whether Δ is big or small The magnitude of the d-orbital splitting (either Δo or Δt) is dependent on the type of ligand The (empirical) ordering of the ligands is governed by the ligand donor atom .> Br.> I- big Δo favours low spin CHEM1010 Transition Metal Chemistry small Δo favours high spin School of Chemistry and Molecular Biosciences .

com/2012/03/25/theopposite-party/ CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .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 Δo) http://www.dxy and dx2-y2 sets Weak field ligands result in a small energy (Δo) difference between the dxy.naomilkoffman.dxz.Blackman p 572 THE UNIVERSITY OF QUEENSLAND AUSTRALIA Strong and Weak Field Ligands Hund’s 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 (Δo) difference between the dxy.dxz.

> I- low spin high spin Strong field e.Blackman p 572 THE UNIVERSITY OF QUEENSLAND AUSTRALIA CN.> en > NH3 ~ py > H2O > C2O42. [Fe(H2O)6]3+ School of Chemistry and Molecular Biosciences .> phen ~ NO2. [Fe(CN)6]3Vitally Important!!!! CHEM1010 Transition Metal Chemistry Weak field e.g.> Cl.g.> S2.> OH.> Br.> F.

minimum number of unpaired electrons (low spin) OR . . .maximum number of unpaired electrons (high spin).Blackman p 568 THE UNIVERSITY OF QUEENSLAND AUSTRALIA 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 . . CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . .

Why? Δt = 4/9Δo (for the same type of ligands) Fewer donor atoms. low spin tetrahedral complexes are NOT found. and poorer overlap with d orbitals Δt is never large enough to enforce electron pairing CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .THE UNIVERSITY OF QUEENSLAND AUSTRALIA Tetrahedral Complexes Unlike the octahedral complexes.

Blackman p 574 THE UNIVERSITY OF QUEENSLAND AUSTRALIA Magnetism Both d6 systems. what are the differences between them? CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

THE UNIVERSITY OF QUEENSLAND AUSTRALIA d6 system No unpaired electrons DIAMAGNETIC d6 system 4 unpaired electrons PARAMAGNETIC Remember: It is “dia” to have all paired electrons. Important terms!!!!! CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .THE UNIVERSITY OF QUEENSLAND AUSTRALIA Magnetic Susceptibility balance Gouy balance schematic. The weight of the sample in a glass tube is measured with or without a magnet present.

THE UNIVERSITY OF QUEENSLAND AUSTRALIA REPELLED ATTRACTED DIAMAGNETIC CHEM1010 Transition Metal Chemistry PARAMAGNETIC School of Chemistry and Molecular Biosciences .

M . = Bohr magnetons This is on the data sheet for the exam. given by a numeric quantity called the magnetic moment (μeff) or spin only magnetic moment (μso) µ eff = N ( N + 2) B.Blackman p 574 THE UNIVERSITY OF QUEENSLAND AUSTRALIA MAGNETISM The number of unpaired electrons (N) . M. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . Important formula!!!!!! B.the degree of interaction with magnetic fields We use a term called magnetic susceptibility.

87 24 = 4. M .83 15= 3.M.THE UNIVERSITY OF QUEENSLAND AUSTRALIA = µ eff Number of unpaired electrons One Two Three Four Five N ( N + 2) B.90 35 = 5. 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 = 2.92 CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . µeff B.

90 B. low spin d4 t2g4 eg N=2 consider: octahedral. M.THE UNIVERSITY OF QUEENSLAND AUSTRALIA consider: octahedral. M. School of Chemistry and Molecular Biosciences . CHEM1010 Transition Metal Chemistry µ eff = N ( N + 2) = 4( 4 + 2) = 4. high spin d4 t2g3 eg1 N=4 µ eff = N ( N + 2) = 2( 2 + 2) = 2.83 B.

Blackman p 570 THE UNIVERSITY OF QUEENSLAND AUSTRALIA Colours of Transition Metal Complexes CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

THE UNIVERSITY OF QUEENSLAND AUSTRALIA Colours of Transition Metal Complexes HEXAAQUA COMPLEXES – [M(H2O)6]2+ Mn(II) Fe(III) Co(II) Ni(II) Cu(II) Zn(II) CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

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. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .Blackman p 570 THE UNIVERSITY OF QUEENSLAND AUSTRALIA Most transition metal complexes are coloured.

THE UNIVERSITY OF QUEENSLAND AUSTRALIA CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

the light transmitted (seen by our eyes) is complementary to the light absorbed.e.THE UNIVERSITY OF QUEENSLAND AUSTRALIA Complementary colours Light not absorbed remains to be detected by our eyes i. opposite on the colour wheel CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

THE UNIVERSITY OF QUEENSLAND AUSTRALIA Sample absorbs all light except that coloured green. red and orange light. Green is perceived. Green is perceived. green and yellow light pass through. Blue. Sample absorbs violet. Important concept!!!! CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

Blackman p 570 THE UNIVERSITY OF QUEENSLAND AUSTRALIA This diagram will be provided in the exam. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . You need to understand how to use it.

3BeO.Al2O3.(Cr2O3).Al2O3.6SiO2 Some of the Al3+ ions in beryl replaced by Cr3+ and the characteristic colour of emerald results.THE UNIVERSITY OF QUEENSLAND AUSTRALIA Transition metal ions and gem stones Emeralds are derived from the mineral bery which is beryllium aluminium silicate 3BeO.6SiO2 CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

THE UNIVERSITY OF QUEENSLAND AUSTRALIA Gem Stones CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

THE UNIVERSITY OF QUEENSLAND AUSTRALIA [Ti(H2O)6]3+ d1 system CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

Important concept CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . Because the complex ion [Ti(H2O)6]3+ absorbs yellow-green light. the emerging light is violet.THE UNIVERSITY OF QUEENSLAND AUSTRALIA When white light shines on a filter that absorbs in the yellow-green region. a solution of it is violet.

THE UNIVERSITY OF QUEENSLAND AUSTRALIA 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 CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

THE UNIVERSITY OF QUEENSLAND AUSTRALIA 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? CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

visible light absorption excites electrons from lower energy d orbitals to higher energy d orbitals. In transition metal complexes. Energy of absorbed light (λ) for one photon is inversely proportional to the wavelength of the light. hc E= λ h = Planck’s 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 λ CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .See page 571 Blackman THE UNIVERSITY OF QUEENSLAND AUSTRALIA Absorption of light must result in some energetic change to the system (excitation).

Blackman p 570 THE UNIVERSITY OF QUEENSLAND AUSTRALIA d1 [Ti(H2O)6]3+ hν Ground state CHEM1010 Transition Metal Chemistry Excited state School of Chemistry and Molecular Biosciences .

Blackman p 570 THE UNIVERSITY OF QUEENSLAND AUSTRALIA hν CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

e.THE UNIVERSITY OF QUEENSLAND d1 AUSTRALIA Recall that Δt = 4/9 Δo. So tetrahedral complexes must absorb at longer wavelengths than octahedral analogues (with similar ligand fields) i. it takes less energy to promote an electron from a lower energy d-orbital to a higher energy d-orbital. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

Blackman p 570 THE UNIVERSITY OF QUEENSLAND AUSTRALIA 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) . CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .usually does not emit light.

As Δo increases.> More energy. CN. more energy is required to promote electrons. longer wavelength School of Chemistry and Molecular Biosciences .THE UNIVERSITY OF QUEENSLAND AUSTRALIA The magnitude of Δo is dependent on the ligand field strength It increases for strong field ligands. meaning shorter wavelength. shorter wavelength CHEM1010 Transition Metal Chemistry H2O > FLess energy.

THE UNIVERSITY OF QUEENSLAND AUSTRALIA CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

> OH.> Br.> phen ~ NO2.THE UNIVERSITY OF QUEENSLAND AUSTRALIA High Energy. UV light Lower energy nm CN.> ICHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .> F.> S2.> Cl.> en > NH3 ~ py > H2O > C2O42.

THE UNIVERSITY OF QUEENSLAND AUSTRALIA 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 Δo (kJ mol–1) <165 166 176 196 206 214 226 239 249 279 292 >299 hc ∆o / t = λ hcA ∆o / t = 1000λ kJ mol-1 (for one mole of photons) CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

− 19 hc (6.087 × 10 − 19 J × 6.087 × 10 J −9 (486 × 10 m) λ − 34 These energies are usually expressed in units of kJ mol-1 so we need to convert this = ∆ 4.02 × 10 mol 23 −1 1 kJ −1 × = 246.Blackman p 571 THE UNIVERSITY OF QUEENSLAND AUSTRALIA Consider that an octahedral Cr(III) complex has an absorption band at 486 nm.626 × 10 J s)(2. Calculate the magnitude of the crystal field splitting for this complex. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .998 × 10 8m s-1 ) ∆ = = = 4.1 kJ mol 1000 J Avogadro constant Divide the number in Joules by 1000 to convert to kJ.

THE UNIVERSITY OF QUEENSLAND AUSTRALIA HEXAAQUA COMPLEXES – [M(H2O)6]2+ Mn(II) Fe(III) Co(II) Ni(II) Cu(II) Zn(II) CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

Blackman p 572 THE UNIVERSITY OF QUEENSLAND AUSTRALIA Zn(II) Colourless – Why? CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

THE UNIVERSITY OF QUEENSLAND AUSTRALIA Zn(II) is d10 d10 The eg orbitals are already full – there is no space to fit a promoted electron. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

Blackman p 572 THE UNIVERSITY OF QUEENSLAND AUSTRALIA Mn(II) Very. very pale pink. Why? CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

d5 This excited state can’t exist – can’t have two electrons with all 4 quantum numbers the same – called spin forbidden.THE UNIVERSITY OF QUEENSLAND AUSTRALIA d5 This configuration can’t occur! X High spin. School of Chemistry and Molecular Biosciences CHEM1010 Transition Metal Chemistry .

561 Blackman THE UNIVERSITY OF QUEENSLAND AUSTRALIA 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. due to formation of [CoCl4]2-.+ 4H2O(l) CHEM1010 Transition Metal Chemistry trans-[CoCl2(H2O)4] + 2Cl-(aq) School of Chemistry and Molecular Biosciences . The Portuguese weather rooster changes colour with the weather. pink trans-[CoCl2(H2O)4] is formed. Portions are coated in cobalt chloride. which respond to changes in humidity. it is blue. In humid conditions. In dry weather. [CoCl4]2.Equilibrium p.

ions added. pink If water is added or Cl. returns the system to equilibrium. if possible. favouring formation of blue [CoCl4]2-.+ 4H2O(l) trans-[CoCl2(H2O)4] + 2Cl-(aq) blue If water is removed or Cl. (p. 364 Blackman) [CoCl4]2. the equilibrium will move to the right.ions removed. favouring formation of pink trans-[CoCl2(H2O)4]2-. the equilibrium will move to the left. the system undergoes a change in a direction that counteracts the disturbing influence and. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .Blackman p 561 THE UNIVERSITY OF QUEENSLAND AUSTRALIA Le Chatelier’s Principle: If an outside influence upsets an equilibrium.

If K is small. “formation constant. Different names. the equilibrium lies to the right (products). the equilibrium lies to the left (reactants). equilibrium constant. association constant. binding constant” all meaning the same thing CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .Blackman p 547 THE UNIVERSITY OF QUEENSLAND AUSTRALIA Equilibrium Constant For the general reaction The equilibrium constant K for the reaction is given by [C] [D] K= a b [A] [B] c d If K is large.

Blackman p 547 THE UNIVERSITY OF QUEENSLAND AUSTRALIA 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” CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

THE UNIVERSITY OF QUEENSLAND
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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+
School of Chemistry and Molecular Biosciences

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

[Ni(H2O)6− x (NH3)x ] βx = [Ni(H2O)62 + ][NH3]x
β - Cumulative formation constants e.g. [Ni(H2O)6]2+ + 3NH3 [Ni(OH2)3(NH3)3]2+ + H2O

[Ni(H2O)3(NH3)32 + ] β3= [Ni(H2O)62 + ][NH3]3
CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences

If βn is small the complex shows little tendency to form. if βn is large the complex forms almost completely. .Blackman p 561-562 THE UNIVERSITY OF QUEENSLAND AUSTRALIA β3 = K1 x K2 x K3 and. in general βk = K1 x K2 x K3 x . CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences . . . x Kk Important concept The magnitude of βn for a complex is a measure of how far the formation reaction for that complex proceeds towards completion.

Ni2+ complexes of the same ligand are more stable than Co(II) complexes.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 THE UNIVERSITY OF QUEENSLAND AUSTRALIA βn 5.0 × 104 2. (CHEM2050 Irving Williams series CHEM1010 Transition Metal Chemistry Mn(II) < Fe(II) < Co(II) < Ni(II) < Cu(II) > Zn(II) ) School of Chemistry and Molecular Biosciences . Here.0 × 1014 4. Cu(II) complexes are generally the most stable of the first row divalent (2+) transition metal ions. when comparing complexes with the same ligands.0 × 108 1.1 × 1017 Conclusion 1: Identity of the metal affects stability.

CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .6 × 1033 1.0 × 104 4.Blackman p 562 THE UNIVERSITY OF QUEENSLAND AUSTRALIA Conclusion 2: Ligands can show different affinities for various oxidation states of the same metal ion.0 × 1014 5. 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 βn 5.0 × 1048 Cobalt(III) is favoured in each case.

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 βn 2.1 × 1017 3. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .0 × 108 4.6 × 1018 The bidentate ligand en results in a more stable complex (larger βn) than the monodentate ligand NH3.Blackman p 563 THE UNIVERSITY OF QUEENSLAND AUSTRALIA Compare the numbers for complexes of monodentate (NH3). compared to the en and NH3 complexes. The hexadentate edta ligand results in the most stable complex (largest βn). Conclusion 3: The number of chelate rings formed affects the stability of the complex. More chelate rings = more stable.

Blackman p 563 THE UNIVERSITY OF QUEENSLAND AUSTRALIA Important concept Complexes containing chelate rings are usually more stable than similar complexes without chelate rings. termed . as the number of chelate rings increases. so does the stability. Generally.THE CHELATE EFFECT CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

Blackman p 563 THE UNIVERSITY OF QUEENSLAND AUSTRALIA Compare: A monodentate system [Ni(NH3)6]2+(aq) + H2O(l) With a chelate [Ni(NH3)5(OH2)]2+ + NH3(aq) CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .

THE UNIVERSITY OF QUEENSLAND AUSTRALIA 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 βn 2. CHEM1010 Transition Metal Chemistry School of Chemistry and Molecular Biosciences .5 × 1041 For EDTA4− we see the effect of both the charge on the metal ion and the chelate effect.8 × 1016 2.

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