Anorganische Chemie

Prof.Dr. Lies Bouwman, EE3.19,  4550

bouwman@chem.leidenuniv.nl

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 Collegerooster en eindcijfer

• 10 hoorcolleges (9 – 11)
• 6 werkgroepen (13:30 – 15:30)
• 2 tussentoetsen (13:30 – 15:30; zonder cijfer)
• 1 oefensessie (13:30 – 15:30; zonder cijfer)
• 1 vragenuur (9 -11)

• Tentamen: 1 juni 2018 (9 – 12; USC) (100%)

• Nabespreken: 1 juni (12:45 – 13:45) C1
• Herkansing: 4 juli (9 – 12)

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 Studiemateriaal
• Inorganic Chemistry, 6th Ed
Weller/Overton/Rourke/Armstrong
• Handouts van colleges (op Bb);
Slides hebben sterren
*** = zeer belangrijk
* = zinvol
geen ster: extra (ondersteunende) informatie

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 Inorganic Chemistry

• Basis en herhaling: Delen van Hfst 1-6

• Coördinatiechemie (basis): Hfst 7
• Symmetrie: Hfst 6
• Verder (delen van) H 9, 20, 21, 22, 25, 26
• Per college zal opdracht gegeven worden om bepaalde
paragrafen te bestuderen.

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 Onderwerpen vs Boek
College, onderwerp
ANO1; Basisbegrippen
ANO2; Geometrie, isomeren,
nomenclatuur
ANO3; Thermodynamica, stabiliteit, HSAB
ANO4; Oxidatietoestanden,
ANO5; Symmetrie
ANO6; LFSE, HS, LS
ANO7; MO diagrammen, elektronentelling
ANO8; Organometaalchemie, katalyse
ANO9; Reactiviteit, substitutie, metals in
life
ANO10; Bioanorganische chemie
VOOR college voorbereiden in 6e editie
§4.6-4.10 (p132-142)
§7.1-7.11 (p209-224); §21.9 (p567)
§7.12-7.15; (p225-230); §4.9 (p139-141)
§9.1 – 9.6 (p273-285); §9.9d (p292-293)
§6.1-6.4 (p188-197)
§20.1 (p515-525); §20.8 – 20.9 (p544-558)
§20.2 (p525-530); §22.1 – 22.5 (p579-587)
§25.1, 25.2 (p728-733); 25.4 (p734-736);
Lezen: §25.5 (736-738); 25.9 (p742);
§21.1-21.3, 21.4a,b,c (p550-559);
Lezen: §27.1 – 27.3 (p820-826)
Nog nader te bepalen. Gebaseerd op H26
§26.8 – 26.12 (p783-807); 26.14 (p 810)

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 Studiemateriaal

• Internetsites
– http://wwwchem.uwimona.edu.jm:1104/courses/IC10Kout.html
– http://www.chem.purdue.edu/gchelp/cchem/
– http://www.ilpi.com/organomet/index.html

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 Research @ MCBIM
Metals in Catalysis, Biomimetics & Inorganic Materials
Catalysis:
-Organometallic Chemistry
-Green chemistry
-Biomass conversion

Materials:
-Luminescent lanthanoids
-Spin crossover
-Molecular switches
Biomimetics:
-Model systems for metalloenzymes
-Metal coordination at lipid bilayers
-Molecular motion

Ligand design & Coordination Chemistry

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 Transition metals

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 Vóórkomen coördinatiechemie

• Overal!
• Life depends on metals!
– Enzymen in het lichaam voeren de meest complexe reacties uit
met behulp van een metaal
• Verf droogt door toevoeging kobalt
• Additieven in voedingsmiddelen
• Additieven in wasmiddelen
• Geneesmiddelen

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 Applications coordination chemistry

• In materialen: selectieve ionenwisselaars voor zware

metalen, corrosiebescherming, magnetische en
elektrische materialmen, verlichting
• In homogene katalyse, zoals groene syntheses, chirale
syntheses
• In geneeskunde, bijv. metaalafvoer (ontgifting), als
geneesmiddel (Bi, Pt, Li), of als diagnostisch middel (bijv.
Tc voor hartscan, Gd voor MRI)

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 Applications: catalysis

CH3OH + CO X

O
CH3OH + CO CH3C−OH
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 Applications: drugs

Kink in DNA after

binding of cisplatin

Cl NH3
Pt
Cl NH3

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 What is special in metals? ***

• Charge on the metal

• Size of the metal ion
• Geometry / preferences
• Ligand binding preferences
• Binding kinetics: reactivity
• Reactivity patterns: redox potential, photoreactivity,
lability, catalysis

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 Chemistry of transition metal compounds

• Complexes and colors

• Reactivity and catalysis
• Magnetism
• Reduction and oxidation
• Biochemistry - bioinorganic

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 What is special in metals? ***

• Non-metals:
– Octet rule
– Use s and p orbitals for binding
– Covalent binding
• Metals:
– 18-electron rule
– Use s, p and d orbitals for binding
– Non-covalent binding

Weaker and more reactive bonds!

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 Dative binding **

“BH3” NH3
B N

1s2 2s2 2p1 1s2 2s2 2p3

H H
sp3 sp3
B N
H H
H H
H H

H H N

BH3—NH3
B

H H

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 Coordination compound ***

• Combination of metal and ligands

• Lewis acid/base combination
• Donor atom = atom bonded to metal
• Coordinate bond = dative bond =
– Donor atom supplies 2 electrons
• Complex = coordination compound
– Coordination sphere
– Coordination number
– Geometry

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 Ligand binding ***

• Ligand: electron lone pair, nucleophilic

• Metal: low-lying empty d-orbitals, electrophilic

• Ligand: electron-pair donor, Lewis base, σ base

• Metal: electron-pair acceptor, Lewis acid, σ acid

M : L

Electron donation

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 Metal complexes *

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 Ligands: electron-pair donors ***

• Ligare (Latin) = to bind

• Atoms, ions, molecules with at least one free, available
electron pair
• Examples:
– Water, ammonia, chloride, hydroxide, acetone, pyridine, carbon
monoxide, cyanide, dihydrogen, dioxygen, hydride, …

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 Drawing structures **

• Coordination bond (2 electrons)

– Usually a “normal” line
– Sometimes an arrow

NH3 NH3
H3N NH3 H3N NH3
2+ 2+ + –
Ni Ni Rh CH3
H3N NH3 H3N NH3
NH3 NH3

NB: Chemsketch has an option for coordinate bond

www.acdlabs.com
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 Monodentate ligands **
N

N NH
N N NH O
N

Imidazole pyridine pyrazine pyrazole thf

tpp, triphenylphosphine
P

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 Chelating ligands

• Chela (Greek: chely) =

great claw of lobster

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 Chelating ligands **

Chelate-ring size
R
Bidentate
4 O O
-
Φ2P PΦ2
dppm

Φ2P PΦ2
5 H2N
en
NH2
N N N N dppe
bpy phen
H3C CH3

6 O
-
O NH2 NH2 Φ2P PΦ2
acac dppp

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 Chelate-ring size ***

R H3C CH3

- -
O O H2N NH2 O O
Φ2P PΦ2

M M M M

4 5 6 7
Coordination angle (approx., depending on M):
60° 80° 88° 95°
• Chelate rings 5 and 6 most stable
• Chelate ring 4: one donor atom semi-coordinating
• Chelate ring 7 and higher: weak, “two monodentates”
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 Chelating ligands ***

H
N
Tridentate
H2N NH NH2
- - Φ2P PΦ2
O O O O PΦ2

O
-
O N N

Tetradentate N
- -
O O
O - -
O O O

Salen (Schiff base)

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 Polydentate ligands **
- -
O O

O O
N N
N N N N
- N N
-
O O

O
edta O
tpen
Na4edta present in commercial products:
Soap; beer; mayonnaise

to "trap" trace amounts of metals that could potentially catalyze the

decomposition of the product
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 EDTA in food
• I am contacting you to make you aware of NineSigma Request, RFS# 50658-1,
"Seeking Natural Chelator for Transition Metals in Food." Although ready-to-
demonstrate commercially available solutions are preferred, R&D proposals would also
be entertained as long as the solution can be realized by 2010. Please respond by
February 22, 2008 with a statement of interest or proposal.
• Our client, a Fortune 500 Global Food Company, is seeking natural, consumer-friendly
ingredient technology to function as a replacement for EDTA
(ethylenediaminetetraacetic acid) in dressings and sauces. EDTA is a water-soluble
ingredient that functions as a chelator for transition metals and is commonly used
alone or in combination with anti-oxidants to provide oxidative stability for food
systems such as dressings and sauces. Performance criteria are detailed below.
• The desired ingredient must:
• Preferably be approved or GRAS (generally regarded as safe) for use in food products
in the US; possibly will consider self-GRAS options if promising
• Provide the same or similar efficacy in chelating transition metals as EDTA
• Be labeled as a natural ingredient
• Replace EDTA – approx. 20,000 lbs./year
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 [M(edta)] complexes

[Mg(edta)(H2O)]2– [Co(edta)]2–
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 X-ray structures

Single crystals CAD4 diffractometer Diffraction pattern

3D coordinates

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 Tripodal ligands ***

Tripous (Greek): “three feet”

N N N
N N
- N
HB N
N
N
N N

HO N

tridentate O
HO

tetradentate
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 Tripodal ligands

N
R1 R1
N

R2 OH HO R2

N O
M
O O/N

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 Macrocyclic ligands **
O
CH3
N S O O
H3C S
N

N S O O
CH3 O
Me3tacn
18-crown-6
H3C CH3
CH3
NH HN O O

NH HN
H3C O O
CH3 CH3

Benzo-12-crown-4
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 [K(18-crown-6)]+

Helps to dissolve e.g. K[MnO4] in apolar solvents!

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 Ambidentate ligands ***

NO2–
NCS– nitrite
thiocyanate O
O N
- 2+
S C N Ni Co N -
O
-
O
- Co
S C N
2+
Ni

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 Bridging ligands ***

Anything with more than 1 lone pair…

R R
N
- -
O O O O
N
M M M M

N N
Cl–, OH–, RS–, etc

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 [Mn4O2(bpy)2(2-ethylhexanoate)6]

Mixed valence!

2 Mn2+
2 Mn3+
6 2-ethylhexanoate
2 bipyridine
2 O2–

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 Summary keywords

• Dative binding, coordination bond, Lewis acid, Lewis base

• Ligand:
– Mono, bi, tri, …, multidentate; ambidentate, bridging, chelating,
tripodal, macrocyclic
– Chelate ring, bite angle

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 Assignment

• Study H7 § 7.1 – 7.11

– p 209 - 224

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 Art from Bela Vizi

Retired coordination
chemist from Hungary

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