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D-block Flashcards

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1
Q

What is a transition metal

A

Elements w/ partially filled d/f-shells

Partially filled d/f-shell in most common compound

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2
Q

How to do you work out the number of d e-

A

No e- = group no. - metal OS

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3
Q

What are the trends in atomic radius

A

General contraction across period
∵ increasing Zeff

Increase from row 1 -> row 2
Row 2/3 metal in a triad
very similar radii
∵ lanthanide contraction
& increasing Zeff
w/ little shielding from ‘core’ 4f14 shell

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4
Q

What are the anomalies in atomic radius

A

Mn
∵ irregular solid state structure

Increase for Cu, Zn
∵ greater e- repulsion

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5
Q

What is the trend in ionic radius

A

Contraction left to right
Decrease Ti 2+ -> Cr 2+
Increase Cr 2+ -> Mn 2+
Decrease Mn 2+ -> Ni 2+
Increase Ni 2+ -> Zn 2+

Irregular
∵ effect d-orbital occupancy

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6
Q

What is the trend in IE

A

General rise across period
∵ increasing Zeff

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7
Q

What are the anomalies in IE

A

Dip for Mn+ -> Mn 2+ & Fe 2+ -> Fe 3+
both d6 -> d5
∴ removing paired e-
∴ experiencing repulsion

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8
Q

What is the trend in electronegativity

A

All relatively low
∵ metallic behaviour

General increase across period

Decrease down triad
in groups 3 -5
increases groups 6 - 12

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9
Q

What is the trend in atomisation energies

A

Higher than s-block metals
more valency e-
∴ stronger metallic bonds

Maxima at groups 5/6
most unpaired e-

Dip group 7
eg. Mn free atom is 3d5 4s2 & irregular structure

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10
Q

What is the trend in melting point

A

Stronger metallic bonding than s-block

Generally increase down group (triad)
larger 4d/5d orbitals
better overlap for bonding

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11
Q

What is an oxophilic metal

A

Metals that tend to be found as oxides

Left of d-block

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12
Q

What are chalcophilic metals

A

Metals that tend to be found as sulphides

Right of d-block

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13
Q

How can you determine max possible OS

A

Max possible OS = group number

High OS less common for Fe - Zn
∵ higher Zeff & IE

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14
Q

How do the OS for row 1 metal halides differ

A

F giver higher metal OS than Cl
∵ more 𝜒

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15
Q

What is the coordination chemistry of a metal cation in aq

A

Complex, hydrated ion
[M(OH2)6]n+

Ligand lewis base - metal lewis acid
∴ dative bond

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16
Q

What is the coordination chemistry of metal sulfate

A

MSO4 –H2O–> [M(OH2)6]n+ + SO4 2-
[M(OH2)6]n+ —> M(OH2)5SO4 crystallise
m(OH2)5SO4 –heat–> MSO4

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17
Q

What is the denticity of a ligand

A

No. donor atoms coordinated to metal

𝜅

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18
Q

What is the coordination number of a metal complex

A

CN = no. donor atoms attached to metal

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19
Q

When are CN > 6 more common

A

3rd row d-block & f-block

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20
Q

What are linkage isomers

A

Ambidentate
eg. NO2 - ligand coordinate through N or O

convert photochemically

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21
Q

What are ionisation isomers

A

Distinguished by chemical test

eg. [Co(NH3)5(SO4)]Br –Ag+–> AgBr
[Co(NH3)5(SO4)]SO4 –Ag+–> no reaction

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22
Q

What are hydrate isomers

A

Coordinated H2O vs. water of crystallisation

eg. [Cr(OH2)6]Cl3 vs.
[Cr(OH2)5]Cl2 . H2O

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23
Q

What are geometrical isomers

Study These Flashcards
A

cis/trans isomers

facial (fac) - 3x z ligands cis to each other
/meridonal (mer) - 2x z ligands cis & 1x z ligand trans to p

24
Q

What are optical isomers

Study These Flashcards
A

Two complexes that are
non-superimposable mirror images
& are enantiomers

25
Why do some d-orbitals experience more repulsion
dz2 & dx2-y2 have lobes pointing along axes ∴ directly towards ligand so more repulsion of e- dxy, dxz & dyz have lobes pointing between axes ∴ less repulsion of e-
26
How do d-orbitals feel repulsion in a tetrahedral geometry
dz2 & dx2-y2 feel repulsion from ligands
27
How does Δt compare to Δo
Δt ≈ 4/9 Δo
28
How do high spin octahedral d-orbitals fill
All 5 d-orbitals singularly occupied before pairing If Δo small e- prefers high spin
29
How do low spin octahedral d-orbitals fill
eg only occupied orbital after t2g filled w/ 6e- If Δo large e- prefers low spin
30
How do tetrahedral d-orbitals fill
High & low spin fill in the same ways as octahedral (3x t2g orbitals at the bottom) Low spin rare ∵ Δt usually small ∴ favours high spin
31
What is the crystal field stabilisation energy
CFSE = change in energy resulting from splitting of d-orbitals CFSE = E (w/ splitting) - E (w/out splitting)
32
What is P in CFSE
Pairing energy due to repulsion between paired e- only count extra pairings due to splitting
33
How does Δo/Δt compare to P
For d4 - d7 low spin if Δo > p high spin if Δo < p For d3 - d6 low spin if Δt > p high spin if Δt < p
34
How do octahedral and tetrahedral complexes compare
O strongly favour for d3, d8, low spin d4 - d7 No CFSE difference for d0, d5 high spin, d10 Small CFSE difference for d1, d2, high spin d6, d7
35
What is the effect of CFSE on hydration enthalpies of M2 ions
ΔhydH generally gets larger across 3d row ionic radius gets smaller clear trend for d0, d5, d10 (0CFSE) Deviation from smooth curve for other ions ∵ additional stabilisation of [M(OH2)6]2+ hydrated ions by CFSE
36
What is ferromagnetism
Electron spins only align below curie temp eg. 1043K for Fe Above critical temp material becomes paramagnetic
37
What affects d-orbital splitting
1. Charge (OS) of metal ion higher +ve change on M n+ increases CFS 2. Position of metal in d-block CFS increases down a group larger 4d/5d orbitals interact more w/ ligands 3. Nature of ligand ligands can be ranked to spectrochemical series v. strong field ligand: CN-, CO strong field ligand: NH3 weak field ligand: H2O, halogens
38
What is the Jahn-Teller effect
Some octahedral complexes 9th e- could go into either dx2-y2 or dz2 Molecule in degenerate electronic state undergo distortion to remove degeneracy Causes further splitting & lowers overall energy
39
What are the distortions for octahedral complexes
1/3 e- in eg orbitals large tetragonal elongation or compression 1/4 e- t2g orbitals small tetragonal compression 2/5 2- in t2g orbitals small tetragonal elongation d3, d8, d10, high spin d5, low spin d6 no distortion
40
When is square planar favoured
For d8 complexes
41
What are the comparisons of 4-coordinate d8 complexes
Square planar gives larger CFSE especially for 2/3 metals Rh(I), Ir(I), Pd(II), Pt(II), Au(III) Tetrahedral minimises repulsion between ligands eg. Ni(II) complexes w/ bulky ligands or weak field ligands Tetrahedral = paramagnetic Square planar = diamagnetic
42
How can wavelength of complexes be calculated
ΔE = hv = hc/𝜆
43
What are the selection rules
1. Laporte Rule For transition to be allowed qn must change by ±1 eg. s -> p or p -> d 2. Spin selection rule e- cannot change its spin during transition 3. Parity selection rule g -> g or u -> u forbidden g -> u allowed
44
Are d -> d transitions allowed
Formally formatted by Laporte in octahedral complexes Molecule w/ polyatomic ligands not perfectly octahedral vibrations mean centre of symmetry can be temporarily lost some mixing of orbital character can occur ∴ d -> d transitions can occur but relatively weak
45
What is the affect of acid reaction of d-block metal ions in aq
Solutions [M(OH2)6]n+ are acidic e- density pulled towards M n+ cation M n+ polarises coordinated H2O O-H polarity increases depends on charge M n+ Proton transfer to solvent H2O raises acidity
46
What happens when base is added to coordinated complexes
Deprotonation of coordinated water ligand (not ligand exchange)
47
What happens when NH3 is added to coordinated complexes
Deprotonation of coordinated water (reversible reaction) In excess NH3 ligand exchange occurs
48
What are the types of ligand substitution
Anation = neutral replaced by anion Aquation = any other ligand replaced by water
49
What are the classifications of kinetics for ligand substitution
Labile = complexes undergo rapid substitution Inert = complexes undergo slow substitution row 2/3 [M(OH2)6]n+ generally more inert
50
What is the K equation for ligand substitution
K = [MX5Yn-][X-] / [MX6][Y-]
51
What is the stability constant
βn = k1 k2 k3 ... kn = [MLn] / [M][L]^n logβn = log (k1) + log (k2) + ... + log (kn)
52
What is the chelate effect
Enhanced stability of complexes containing chelate ligands (eg. polydentate) over one containing similar monodentate ligands
53
How is ΔG calculated from the stability constant
ΔG = -RT x lnβ ΔG = -RT x ln10 x logβ
54
What is the macrocyclic effect
Complexes of macrocyclic ligands show even greater stability Donor atoms 'pre-organised'
55
What is the effect of chelate ring size on stability
As chelate ring size increase logK generally decreases largest k = most stable
56
What is the Irving-Williams series
Trend of logβ where M is different metal ions Peaks in -CFSE/Δo for d3 and d8 Trough for d0, d5, d10 ∵ decreasing ionic radius left -> right trend in CFSE for d5 -> d10 larger Δo in product [M(en)3]2+
57
What are the interactions between hard/soft acids/bases
Hard acid-hard base interactions more electrostatic in character dominated by +/- charges Soft acid-soft base interactions more covalent in character dominated by interactions of donor/acceptor orbitals

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