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CHEM214 > For Catalysis > Flashcards

For Catalysis Flashcards

1
Q

Which types of d orbitals are often low spin and so are likely to be soft?

A

4d and 5d

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2
Q

What ligands must Ni have to be square planar? What shape is it with the other type?

A

Strong field ligands, tetrahedral with weak field

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3
Q

What field strength is Cl as a ligand?

A

Weak field = pi-donor

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4
Q

What field strength is PPh3 as a ligand?

A

Weak field

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5
Q

What are the isomers for square planar always?

A

Cis and trans

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6
Q

What is a high spin orbital?

A

Half filled with e-

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7
Q

What are the isomers for a metal of 2 ligands with 3 of each?

A

Fac and mer

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8
Q

How is a mer isomer positioned?

A

180deg between the two ligands furthest away from each other (similar to trans)

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9
Q

How is fac isomer positioned?

A

All of the ligands of the same type are on the same face (similar to cis)

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10
Q

What are the isomers for a metal with 2 of one ligand and 4 of another ligand?

A

Cis and trans

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11
Q

What is the en ligand?

A

BIDENTATE

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12
Q

What is the difference between enantiomers and isomers?

A

Enantiomers = optical with the different shaped bonds
Isomers = position of atoms

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13
Q

Eq for metal oxidation state?

A

Overall charge on the complex - total formal charge on the ligands

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14
Q

What makes a ligand soft?

A

Large ionic radii as they’re further down the periodic table and less electronegative

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15
Q

What makes a ligand hard?

A

Very electronegative and 3d

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16
Q

Are hard-soft or hard-hard/soft-soft interactions favoured?

A

Two of the same

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17
Q

When are e- paired vs promoted?

A

Paired = large deltaOct
Promoted = small deltaOct

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18
Q

What makes deltaOct small?

A

Weak field ligands

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19
Q

What makes deltaOct big?

A

Strong field ligands

20
Q

What is the orbital distortion for d1?

A

dxy and dx^2-y^2 move down in energy and the electron goes in dxy

Compression

21
Q

What is the orbital distortion for d3?

A

No distortion bc all 3e- are at the same energy level anyway

22
Q

What is the distortion for high spin d5?

A

No distortion bc high spin so all orbitals are half filled

23
Q

What is the distortion for low spin d7?

A

Compression

dz^2 and dx^2-y^2 go down,

24
Q

What is the distortion for high spin d7?

A

Elongation

dz^2 goes down and dxy goes up

25
Q

What field type is H2O ligand?

A

Weak field

26
Q

What is the distortion for d8?

A

No distortion bc pairing so e- paired at the bottom

27
Q

What colour is high spin d5 and why?

A

Colourless bc all d-orbitals are filled with an unpaired e-

Colour is disallowed if the spin of an e- would need to be changed upon promotion

28
Q

When is a complex diamagnetic?

A

All e- are paired - the spins cancel out so no magnetism

29
Q

What colour is d0?

A

Colourless bc no e- to promote and so no d<->d transitions

30
Q

What makes something paramagnetic?

A

Unpaired e- so complex has colour bc d<->d transition can occur upon promotion

31
Q

What makes something high spin?

A

Weak field ligand

32
Q

What shape does d3 favour?

A

Octahedral

33
Q

What arrangement are Pd(II) complexes nearly always?

A

Square planar

34
Q

What gives something a higher pKa?

A

1) More neutral ligands (e.g. CO) to stabilise the negative charge when a proton leaves and the most stable conjugate base gives a stronger acid

2) A more protic/electronegative metal so the proton is removed more readily

3) If the COMPLEX is negatively charged as it will be unfavourable for it to become more negatively charged by removal of a proton, so the eqm will lie towards this species (acidic)

35
Q

Why do tetrahedral Ni complexes appear blue?

A

Bc deltaTet is small so the adsorption bands are in the red region of the UV spectrum

36
Q

Are there any isomers for MA2B2 complexes?

A

No

37
Q

What does a large deltaOct mean?

A

Small p = paired e- (low spin)

38
Q

What does small deltaOct mean?

A

P is big so high spin (promoted e-)

39
Q

What is elongation?

A

z components to down in energy

x and y components go up in energy

40
Q

What is compression?

A

z components go up in energy
x and y components go down in energy

41
Q

spin only formula

A

S = ¬n(n+2)
where n = no. of unpaired e-
S = total unpaired e- spin

42
Q

what are reduction and oxidation in terms of e-

A

reduction = addition of e-
oxidation = removal of e-

43
Q

how do pi donors and acceptors affect the value for deltaOct?

A

pi acceptor = increases deltaOct

pi donor = decreases deltaOCt

44
Q

how do hard/soft ligands affect deltaOct?

A

hard = increases deltaOct

soft = decreases deltaOCt

45
Q

why are d4, high spin d6, and d9 complexes dissociative?

A

bc they have longer axial bonds which means that the ligands in the dissociative positions dissociate/ are more readily displaced

46
Q

what mechanism is given by negative entropy (S)?

A

associative

CHEM214 (2 decks)

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