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CHEM214 > CHEM214 > Flashcards

CHEM214 Flashcards

1
Q

What are all of the d orbital labels?

A

dxy, dxz, dyz, dz^2, dx^2-y^2

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2
Q

How many d orbitals are there?

A

5

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3
Q

Which orbitals are negative in dxy?

A

those between the x&y axis

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4
Q

Which orbitals are negative in dxz?

A

lobe on the top right along that diagonal

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5
Q

Which orbitals are negative in dyz?

A

lobe on the top left and along diagonal

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6
Q

Which orbitals are negative in dx^2?

A

central lobe

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7
Q

Which orbitals are negative in dx^2-y^2?

A

along the y axis

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8
Q

How are negative orbitals presented in diagrams?

A

shaded = negative

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9
Q

What is the difference between shielding and penetration?

A

shielding = the inner shell core e- shield the nucleus, penetration = the outer e- penetrate the inner shells

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10
Q

What electrons does shielding affect? Why?

A
  • 1s has high ed so shields the 3d e- (and the rest of the orbitals) from the nucleus
  • 2s shields 3d from the nucleus because the 3d maximum lies outside the 2s maximum
  • the 4s does NOT shield 3d from the nucleus much because it is penetrating
  • all s orbitals penetrate the core
  • 4f electrons DO NOT shield 5s
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11
Q

What electrons does penetration affect?

A
  • the 3d penetrates the 2s
  • 3d penetrates 4s very effectively due to lower principle quantum number and the 3d maximum lying inside the 4s maximum
  • the 4s penetrates the core very effectively
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12
Q

How does shielding and penetration depend on radial maxima?

A
  • shielding occurs when the maximum of one orbital lies within the maximum of another
  • small peaks in ed close to the nucleus allow an orbital to penetrate the core
  • the higher the principle quantum number the less shielding an orbital is
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13
Q

What is the effect of penetration?

A
  • the outer electrons experiencing a higher than expected effective nuclear charge, which decreases the orbital energy
  • the orbital doing the penetrating decreases in energy
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14
Q

Does 3d or 4s fill first?

A

4s bc it’s at a lower energy

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15
Q

What makes a transition metal a transition metal?

A

Its partially filled d shell

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16
Q

What is the effect of a half-filled d shell?

A

extra stability

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17
Q

Are 4s or 3d electrons lost first upon ionisation? Why?

A

4s bc at a higher energy due to the 3d penetrating the 4s so the 3d are at a lower energy

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18
Q

What is the d-electron count?

A

the same as valence electron count - total of all electrons in the 3d and 4s orbitals

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19
Q

Equation for d-electron count?

A

group number - oxidation state

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20
Q

What are the pseudo transition metals? Why?

A

Sc, Cu and Zn, Cu has an incomplete d shell, but their chemistry is treated as if they are

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21
Q

What is effective nuclear charge?

A

the amount of nuclear charge seen by an electron in that orbital

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22
Q

What does the effective nuclear charge depend on?

A

the principle quantum number, shielding, and penetration

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23
Q

What is the effect of the effective nuclear charge?

A

as Zeff increases, the orbital energy decreases

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24
Q

What is the effect of shielding?

A

the Zeff of the e- being shielded decreases, so orbital energy increases

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25
Q

What is the pattern of ion size across a period? Why?

A

ionic radius decreases across a period bc the Zeff increases

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26
Q

Why do Mn, Fe, and Ni have higher ionic radius than expected?

A

effect of the partially filled d shell

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27
Q

Why do 2nd and 3rd series elements have similar ionic radii?

A

lanthanide contraction - poor shielding of 5d e- by 4f`as the 4f orbitals are too diffused, 5d penetrate 4f very effectively so 5d has higher Zeff and contracts

28
Q

Are ligands lewis acids or bases?

A

lewis bases (electron pair donors)

29
Q

Are the metal atoms lewis acids or bases?

A

lewis acids (electron pair acceptors)

30
Q

How many electrons do the donor groups of ligands donate?

A

2

31
Q

What is the acetonitrile ligand?

A

MeCN

32
Q

What is the cyano ligand?

A

[CN-]

33
Q

What is the thiocyanate ligand?

A

[NCS]-

34
Q

What is the denticity?

A

the number of bonded groups in a ligand

35
Q

How many e- donated for bidentate ligands?

A

4e-

36
Q

Equations for calculating number of e- donated by a ligand?

A

=denticity2
OR
=number of donor groups2

37
Q

What is the hapticity?

A

The number of atoms in the ligand, bonded to the metal

38
Q

How do pi-bonded benzene and sigma-bonded Ph donate different no. of e-?

A

pi-bonded benzene = 2e- from each bond = 6e-

sigma-bonded Ph = 2e- only from one of the C not the C=C

39
Q

Charge of ammonia?

A

zero

40
Q

What is triethylphosphite?

A

P(OEt)3

41
Q

Charge of ethyl and phenyl?

A

-1

42
Q

What is polarizability?

A

how easy it is to distort the electron distribution/cloud of the donor

43
Q

Equation for charge density?

A

= charge/SA

44
Q

how polarisable is a hard ligand?

A

non polarisable (small, with a high charge, high oxidation state)

45
Q

how polarisable is a soft ligand?

A

highly polarisable (large, with a low charge, low oxidation state)

46
Q

What is the pattern with charge density and polarity?

A

higher charge density = the atom/ion is less polarisable and more polarising

47
Q

Are oxygen donors hard or soft?

A

hard

48
Q

Are phosphorus and sulfur donors hard or soft?

A

soft

49
Q

Is nitrogen hard or soft?

A

depends: ammonia = hard, pyridine = intermediate/soft (part of an unsaturated system)

50
Q

What are the typically hard metal ions?

A

first series TM with (III) oxidation state except Mn(II), Zn(II), and Ti(IV), Hf(IV), V(IV)

51
Q

Why is Ti(IV) a hard metal ion?

A

half-filled d shell (d5)

52
Q

What are the typically hard ligands?

A

F & Cl, H2O, [OH]-, ROH, R2O, [RCO2]-, [SO4]2-, [NO3]-, NH3, RNH2

53
Q

What are the typically intermediate metal ions?

A

1st series TM: Fe(II), Co(II), Ni(II), Cu(II)

Rh(III), Ir(III), Ru(III), Os(III)

54
Q

What are the typically intermediate ligands?

A

Br-, pyridine, [NCS]- = when binding through N

55
Q

What are the typically soft metal ions?

A

Cu(I), Ag(I), Au(I), Hg(II), Cd(II), Pd(II), Pt(II)

56
Q

What are the typically soft ligands?

A

I-, [CN]-, CO, PR3, RSH, R2S, [NCS]- = when binding through S

57
Q

Charge on CO?

A

neutral

58
Q

When is [NCS]- intermediate or soft?

A

intermediate if bonding through N, soft if bonding through S

59
Q

When is [NCS]- intermediate or soft?

A

intermediate if bonding through N, soft if bonding through S

60
Q

What type of ligand is CO?

A

Pi-acceptor so strong field

61
Q

What are some bidentate ligands?

A

acetoacetonate (acac), ethandioate, ethylenediamine

62
Q

how many e- do bidenentate ligands donate?

A

4e-

63
Q

how many e- do monodentate e- donate?

A

2e-

64
Q

how can carboxylate ligands bind?

A

either via one or both oxygens

65
Q

what spin a d e- is Co(III)

A

low spin d6 and high CFSE

CHEM214 (2 decks)

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