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Inorganic Chemistry > transition metal complexes part 1 > Flashcards

transition metal complexes part 1 Flashcards

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1
Q

what are ligands?

A

Lewis Base
Electron donors

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2
Q

what are metal centers?

A

Lewis Acids
Electron acceptors

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3
Q

Adduct

A

the product of a Lewis acid-base reaction

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4
Q

coordination number

A

number of ligand binding sites on metal center

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5
Q

coordination sphere

A

central metal and ligands that are closely attached to it are enclosed in a square bracket

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6
Q

most transition metal complexes are either # or # coordinate
CN= #

A

4 or 6
CN=2

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7
Q

multi-dentate ligands
dentate - greek for ?

A

ligands that can bind through multiple donor atoms
greek for tooth

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8
Q

ligands that stabilize low oxidation state

A

CO, CN-, [Fe(CO)5]

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9
Q

ligands that stabilize normal oxidation states

A

water, ammonia, halides, [Fe(H2O)6]2+, Fe(H2O)6]3+

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10
Q

ligands that stabilize high oxidation state

A

fluoride, oxide [CoF6]2-, [FeO4]2-

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11
Q

ligands can stabilize low oxidation metal centers, but it is not possible with…
stable compound with iron(0):
? compounds cannot be formed:

A

not possible with main group metals
Fe(CO)5
Ca(0)… Ca(CO)5

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12
Q

interesting magnetic properties
NiCl4 2-
Ni(CN)4 2-

A

paramagnetic Ni2+ complex
diamagnetic Ni2+ complex

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13
Q

interesting optical properties
cis-Co(NH3)4Cl2
trans-Co(NH3)4Cl2

A

green
violet

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14
Q

interesting electrical properties
cannot conduct electricity
conducts electricity

A

NiO2
TiO2

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15
Q

Valence bond theory:

A

hybridization of orbitals

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16
Q

each covalent bond is formed by…
the individual orbital identity is…
the bond strength is…

A

an overlap of atomic orbitals from each atom
retained
proportional to the amount of orbital overlap

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17
Q

Bonding in coordination compounds

A

Valence bond theory
filled orbital on ligand
empty orbital on metal cation

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18
Q

the original atomic orbitals are mixed together and transformed into a new set of ? that match the ? for bonding

A

hybrid orbitals
directional requirements

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19
Q

a drawback of the valence bond theory

A

VB theory can ‘t explain color and magnetism of coordination compound

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20
Q

crystal field theory

A

the d-orbitals are degenerate in free atoms
all orbitals have the same energy

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21
Q

upon entering a repulsion field, the d-orbitals…

A

lose their degeneracy

22
Q

incoming ligands ? electrons in orbitals

A

repel

23
Q

the closer the proximity of the ligands…

A

the more repulsion

24
Q

ligands directed between orbitals have

A

low energy

25
Q

orbitals facing incoming ligands

A

high energy

26
Q

incoming ligands generate an ? on the ?

A

“electronic repulsion field” on the transition metal orbitals

27
Q

octahedral field

A

six ligand donor atoms approach in an Oh symmetry

28
Q

four ligand donor atoms approach in an Td symmetry

A

tetrahedral field

29
Q

dxy, dxz, dyz face between …

A

incoming ligands and relative energy decreases

30
Q

dx2-y2 and dz2 face directly at …

A

incoming ligands and relative energy increases

31
Q

eg

A

dx2-y2 and dz2 orbitals

32
Q

t2g

A

dxy, dxz, and dyz orbitals

33
Q

factors that affect crystal field splitting

A

the identity of the transition metal
oxidation state of metal
number of ligands, more ligands, more splitting
nature of the ligands

34
Q

I- < Br- < Cl- < F- < OH- < OH2 < NH3 <en < CN- < CO

A

spectrochemical series
weak field/high spin to strong field/ low spin

35
Q

strong field case
weak field case

A

the splitting energy is large
the splitting energy is small

36
Q

low spin complexes tend to be ? while high spin complexes tend to be ?

A

diamagnetic
paramagnetic

37
Q

d5 metal in gas phase
d5 metal in weak field
d5 metal in strong field

A

5-fold degeneracy
weak field: high spin
strong field: low spin

38
Q

electron pairing energy more than splitting energy
electron pairing energy less than splitting energy

A

high spin
low spin

39
Q

d1-d3 and d8-d10

A

the number of unpaired electrons are the same for strong and weak fields

40
Q

the number unpaired electrons are not equivalent between strong and weak fields

A

d4-d7

41
Q

d0 and d10

A

the transition metal acts like a main-group metal

42
Q

crystal field stabilization energy: the lower energy orbitals are more stable than the …
electrons in t2g orbitals
the net change in orbital energies after splitting is

A

higher energy orbitals
impart extra stability
zero

43
Q

what is Dq?

A

differential quanta which comes from quantum mechanics

44
Q

each electron in t2g decreases energy by
each electron in eg increases energy by

A

4/10
6/10

45
Q

tetrahedral complexes
t2g orbitals are ? by incoming ligands
eg orbitals are ? by incoming ligands

A

repelled
not repelled

46
Q

tetrahedral ligand field splitting is … octahedral ligand field splitting
always ? field

A

opposite
always weak field

47
Q

electrons in the incompletely filled d orbitals can be …

A

excited from lower occupied to higher unoccupied orbitals

48
Q

delta = hc/wavelength

A

the frequency of the absorption is proportional to the crystal field splitting

49
Q

when the excited state relaxes to the ground, ?

A

light is emitted

50
Q

what are the drawbacks of crystal field theory?

A

-considers only the metal ion d orbitals and give no consideration at all to other metal orbitals like s,p
-unable to account for the relative strength of ligands
-bond between metal and ligands purely ionic. it gives no account to partial covalent nature of the metal-ligand bond

Inorganic Chemistry (5 decks)

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