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Lizzie's core 4 > Metal ligand bonding > Flashcards

Metal ligand bonding Flashcards

1
Q

What is the ligand charge of NO (linear)?

A

+1

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2
Q

What is the ligand charge of CO?

A

0

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3
Q

What is the ligand charge of NR3?

A

0

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4
Q

What is the ligand charge of PR3?

A

0

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5
Q

What is the ligand charge of N2?

A

0

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6
Q

What is the ligand charge of O2?

A

0

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7
Q

What is the ligand charge of H2?

A

0

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8
Q

What is the ligand charge of alkenes?

A

0

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9
Q

What is the ligand charge of arenes?

A

0

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10
Q

What is the ligand charge of water?

A

0

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11
Q

What is the ligand charge of H?

A

-1

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12
Q

What is the ligand charge of CH3?

A

-1

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13
Q

What is the ligand charge of F, Cl, Br or I?

A

-1

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14
Q

What is the ligand charge of CN?

A

-1

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15
Q

What is the ligand charge of NO2?

A

-1

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16
Q

What is the ligand charge of NR2?

A

-1

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17
Q

What is the ligand charge of NO (bent)?

A

-1

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18
Q

What is the ligand charge of O?

A

-2

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19
Q

What is the ligand charge of S?

A

-2

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20
Q

What is the ligand charge of NR?

A

-2

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21
Q

What is the ligand charge of N?

A

-3

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22
Q

What is the ligand charge of P?

A

-3

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23
Q

Oxidation state =

A

charge on complex - sum of ligand charges

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24
Q

d electron count =

A

group number - oxidation state

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25
Q

TVEC =

A

d-electron count + electrons donated by ligands + number of metal-metal bonds

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26
Q

Number of electrons donated by CO?

A

2

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27
Q

Number of electrons donated by RCN?

A

2

28
Q

Number of electrons donated by NR3 (amines)?

A

2

29
Q

Number of electrons donated by PR3 (phosphines)?

A

2

30
Q

Number of electrons donated by N2?

A

2

31
Q

Number of electrons donated by O2?

A

2

32
Q

Number of electrons donated by alkenes?

A

2

33
Q

Number of electrons donated by H2O?

A

2

34
Q

Number of electrons donated by H-?

A

2

35
Q

Number of electrons donated by CH3- (or any alky or aryl group, R)?

A

2

36
Q

Number of electrons donated by F-, Cl-, Br-, I-?

A

2

37
Q

Number of electrons donated by CN-?

A

2

38
Q

Number of electrons donated by (NR2)- (bent)?

A

2

39
Q

Number of electrons donated by (η1-C5H5)-?

A

2

40
Q

Number of electrons donated by R2PCH2CH2PR2 (bis-phosphines)?

A

4

41
Q

Number of electrons donated by η4-dienes?

A

4

42
Q

Number of electrons donated by (NR2)- (linear)?

A

4

43
Q

Number of electrons donated by (CH3CO2)-?

A

4

44
Q

Number of electrons donated by (NR)2- (bent)?

A

4

45
Q

Number of electrons donated by (S)2-?

A

4

46
Q

Number of electrons donated by (η5-C5H5)-?

A

6

47
Q

Number of electrons donated by η6-C6H6?

A

6

48
Q

Number of electrons donated by (NR)2- (linear)?

A

6

49
Q

Number of electrons donated by (O)2-?

A

6 (if triple bond), 4 (if double bond). Either is allowed in the exam.

50
Q

Number of electrons donated by (N)3-?

A

6

51
Q

Number of electrons donated by (P)3-?

A

6

52
Q

Enthalpic properties that effect complex formation?

A

Number and strength of M-L bonds, steric factors, Charge of the complex, electronic configuration. Can you expand on each of these?

53
Q

Entropic properties that effect complex formation?

A

Number and size of chelate rings ( 5&6 memebered rings most stable as less ring strain) and solvation ( requirement for an ordered solvent cage lowers entropy)

54
Q

What are the 3 conditions of M-L bonding?

A

1) Orbitals must be of same symmetry to interact ( determines energy of interaction)
2) Must be same E orbitals (determines energy of interaction)
3) Must be physically in the same region of space (must overlap - determines if M-L is even possible.

55
Q

Why is 18 electrons most stable? And what is special about sq. planar complexes?

A

18 electrons fills all the bonding MOs. Anymore and you start to fill the antibonding MOs. For sq. planar, 16 e- complexes are common/sometimes favored, when d8.

56
Q

What types of ligands are these?

H, CH3 (any alkyl or aryl), H2O, NH3

A

siqma donors

57
Q

What types of ligands are these?

CO, CN, H2, Alkenes, N2, O2, PR3

A

sigma donros, pi acceptors (pi acids)
note that PR3 even though it is in the same group as N, PR3 ligands are pi acceptors. PR3 ligands are great, can stabilise low metal ox. states with strong pi accepting and stabilise high metal ox. states with strong sigma donation.

58
Q

What types of ligands are these?
Halides, oxides, sulphides, OR, SR, N (these are all ‘ides’
and NR2, NR, P

A

sigma donors, PI donors.

59
Q

What is synergic bonding? What type of ligand does this?

A

Sigma donation and pi accepting reinforce eachother as the ligand both gives and acdepts electrons, strengthening the bond. pi donor, sigma donors dont have synergic bonding as they are not accepting and donating, only donating. same for sigma donors.

60
Q

What effect do pi donors have on the chemistry of metal complexes?

A

t2g orbitals have raised in E and have more pi* character than in the sigma only case. This REDUCES Δoct. For pi donors, the pi t2g orbitals become slightly antibonding, and so filling these is less energetically favourable than for the non bonding sigma only t2g orbitals, or the bonding t2g pi orbitals of pi acceptor ligands.

61
Q

What effect do pi acceptors have on the chemistry of metal complexes?

A

The t2g orbitals lower in E and are now pi bonding, INCREASING Δoct.

62
Q

Why does filling eg orbitals make ;ligands more labile?

A

because eq orbitals are sigma* orbitals. ANTIBONDING.

63
Q

What is a labile complex?

A

Equilibriates faster than a minute. examples are:

d10 complexes

64
Q

What is an inert complex?

A

Survives for at least a minute. examples are:
d3 and low spin d6 configurations
4d and 5d complexes as they have high CFSE and better M-L overlap

65
Q

What is the d electron count of most sq planar complexes?

A

d8

66
Q

why are h kinetics of first row d block TM complexes much faster than the others?

A

Because the trend in bond strengths is opposite to that of the p block. The more diffuse the orbital, the bigger the overlap and so the stronger the bond. Therefore first row d block have weaker bonds and are therefore kinetically more labile and react faster.

67
Q

Why cant you use the rate equation to determine what mechanism ligand substitution happens by in octahedral complexes?

A

There is a masking of concentration dependence of the incoming ligand in aqueous solution as [H2O] is so large. Therefore, in water or other high conc. solvents, a psuedo first order rate equation happens, and the equation for associative and dissociative mechanisms are identical.

Lizzie's core 4 (3 decks)

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