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Core Chemistry 1A - Paper 2 > Coordination > Flashcards

Coordination Flashcards

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1
Q

Transition metal definition

A

An element with an unfilled d- or f-orbital in at least one common oxidation state

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2
Q

Definition of complex

A

Positively charged central ion (possibly neutral), an acceptor, surrounded in a symmetrical manner by a shell of ions or molecules call ligands

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3
Q

Ligands are held to metal via…

A

dative bonds

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4
Q

Monodentate ligand definition and examples

A

Has one donor atom

eg OH2, Cl-, CN-

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5
Q

Bidentate ligand definition and examples

A

Has two donor atoms

eg bipy, acac-, en, dppe

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6
Q

Tridentate ligand definition and examples

A

Has three donor atoms

eg dien, terpy

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7
Q

Tetradenate ligand definition and examples

A

Has four donor atoms

eg tren, trien

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8
Q

Hexandentate ligand deifnition and examples

A

Has six donor atoms

eg [EDTA]4-

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9
Q

What is chelation?

A

Formation of complexes by chelate ligands

Simultaneous bonding of multiple donor atoms by forming rings around the central atom

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10
Q

Definition and examples of ambidentate ligands

A

Can bond with different atoms depending on metal and conditions
eg SCN- (thiocyanate) and NCS- (isothiocyanate)
NO2- (nitro) and ONO- (nitrito)
Special case CN- in prussion blue:
links through Fe(II) - C - N - Fe(III)

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11
Q

Possible shapes of complexes of metals with coordination number 4

A

Tetrahedral, square planar

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12
Q

Possible shapes of complexes of metals with coordination number 6

A

Octahedral

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13
Q

Possible shapes of complexes of metals with coordination number 5

A

Trigonal bipyramid, square-based pyramid

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14
Q

Order to put things in when writing metal complex formula

A

In square brackets, [ ], cation then anion
Metal ion first
Anionic ligands next (alphabetical)
Neutral ligands (alphabetical)

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15
Q

Types of isomerism

A 
Ligand
Linkage
Ionisation
Hydrate
Coordination
Polymerisation
Geometric
Optical
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16
Q

What is ligand isomerism?

A

Confined to organic ligands

- isomers of the ligand e.g. ortho, para,meta

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17
Q

What is linkage isomerism?

A

For ambidentate ligands only

- bonding with different atoms to central ion

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18
Q

What is ionisation isomerism?

A

Possible in compounds with a complex ion and counter-ion (also a ligand)
eg [PtCl2(NH3)4]Br2 and [PtBr2(NH3)4]CL2

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19
Q

What is hydrate isomerism?

A

Possible with water in or out of coordination sphere

eg [Cr(OH2)6]Cl3 and [CrCl(OH2)5]Cl2·H2O and [CrCl2(OH2)4]Cl·2H2O

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20
Q

What is coordination isomerism?

A

Possible for compounds made up of both cationic and anionic complex ions
Neutral species NOT allowed
eg Cr(NH3)6Cr(CN6)
and [Cr(CN)2(NH3)4]+[Cr(CN)4(NH3)2]-

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21
Q

What is polymerisation isomerism?

A 
Multiply the molecular formula by 2, 3 etc
If oxidation number is +2, up to 3x
If +3, up to 5x
If +4, up to 7x
Only works if all ligands are on metal
22
Q

What is geometric isomerism?

A

Ligands bonded in a different order to the central metal ion

eg cis and trans

23
Q

What is optical isomerism?

A

non-superimposable mirror images

24
Q

Describe stability of complexes for reaction

M-L + L* M-L* + L

A

If reaction goes to RHS, L* makes a more stable complex with M than L

25
Q

What are hard acids?

A 
Most metals in normal oxidation states
H+
All electropositive metals
Have small atomic radius
High effective nuclear charge
High charge-to-radius ratio
High energy LUMO
26
Q

What are soft acids?

A

Cu(I), Rh(I), Ag(I), Au(I)
Pd(II), Pt(II), Cd(II), Hg(III), Au(III)
Have lower charge-to-radius ratio

27
Q

What are hard bases?

A

Have low energy HOMO
F-, OH-, NH3, OH2, N
NO3-, SO4(2-)
ox(2-), CO3(2-)

28
Q

What are soft bases?

A

Br-, I-, S, P

H-, C2H4, CN-

29
Q

Most stable complexes formed are…

A

A hard acid with a hard base

A soft acid with a soft base

30
Q

Assumptions made in Crystal Field Theory

A

Central metal ion = point positive charge
Ligands regarded as dipoles or anions
Ligands = point negative charges
Ionic lattice built from point positive and negative charges
Ionic bonding = electrostatic forces

31
Q

d^n configuration =

A

No of electrons for ‘framework’

= group no. - oxidation state

32
Q

Rules for electron filling

A

Electrons prefer to occupy orbital of lowest energy

Hund’s rule - if there is more than one degenerate orbital, electrons first occupy separate orbitals with parallel spins

Pauli Exclusion Principle - no more than 2 electrons can occupy a single orbital. If 2 electrons occupy a single orbital the spins must be paired

Energy is required to pair 2 electrons in a single orbital, the energy penalty for pairing 2 electrons = pairing energy, P

33
Q

What is Δo and what factors affect its size?

A

As charge on metal increases, Δo gets larger
Δo(1st row) >∆o(2nd row) > ∆o(3rd row)
Stronger field ligands –> larger ∆o

34
Q

Strongest field ligands

A

CN-, CO, PR3, NO2-

35
Q

Weakest field ligands

A

I-, Br-, SCN-, Cl-

36
Q

Describe octahedral crystal field splitting energy, ∆o

A

The energy between the lower dxy, dyz, dxz and higher d(z^2), d(x^2-y^2)
When ligands bond to the metal ion, the orbitals have different energies

37
Q

Name of ligand: OH2

A

Aqua

38
Q

Name of ligand: N2

A

Dinitrogen

39
Q

Name of ligand: O2

A

Dioxygen

40
Q

Name of ligand: NH3

A

Ammine

41
Q

Name of ligand: CO

A

Carbonyl

42
Q

Name of ligand: NO

A

Nitrosyl

43
Q

Name of ligand: Cl-

A

Chloro

44
Q

Name of ligand: Br-

A

Bromo

45
Q

Name of ligand: OH-

A

Hydroxo

46
Q

Name of ligand: CN-

A

Cyano

47
Q

Naming complexes: if ligand already has prefix but there are more than 1 of them e.g. (dioxygen)2 use…

A

bis, tris, etc

48
Q

Order of ions when naming complexes

A

Cation, then anion
Ligands are listen alphabetically before the metal (excluding prefixes)
Include oxidation number of metal
For anionic complexes add ‘ate’ to name

49
Q

Name of ligand: PPh3

A

Triphenylphosphine

50
Q

When is an octahedral complex low spin and high spin?

A

∆o high –> low spin

∆o low –> high spin

51
Q

First row of d-block

A

Proton numbers 21-30

groups 3 - 12

52
Q

How to work out group from top element

A

If in d-block: +18 for second element, +32 for third

Rest of table: +8 for second element, +18 for third, +18 for fourth, +32 for fifth

Core Chemistry 1A - Paper 2 (6 decks)

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