Outline Answers January 2006 IIA Inorganic

Model Answers 2.I1 Main Group Chemistry Answer part (a) and THREE parts from (b) to (e).

(a)

(i) With balanced equations, illustrate a plausible (multistep) synthesis of (CH3CH2)3SnCl from Li metal, CH3CH2Br and SnCl4. (5 marks)

Answer 2Li + EtBr 4EtLi + SnCl4 3Et4Sn + SnCl4

EtLi

LiBr

Et4Sn + 4LiCl 4Et3SnCl

Last reaction requires high temperature to cause redistributuion. Half credit given for 3EtLi + SnCl4. (ii) At room temperature, (CH3CH2)3SnCl exists as a chloride-bridged polymeric solid. In contrast, (CH3CH2)3SiCl is a distillable liquid. Indicating the correct coordination geometry, sketch the structures of both compounds and discuss the factors that explain this structural difference. (5 marks) Answer
Et * Cl Et Sn Et Cl * Et Cl Si

Et Et

Et3SnCl 5 coordinate tin Cl-bridged 1-D polymer Et3SiCl tetrahedral monomer Sn larger and more electropositive. Hence, more inclined to expand coordination sphere.

(b)

Compare the structures of Be(CH3)2 and BeCl2 in the gas and solid-states. Comment upon the bonding in all cases. (5 marks)
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Answer Gas phase. Both structures linear, two coordinate (sp hybridized), simple VSEPR rationale. Solis-state. Both are linear polymers containing four coordinate Be. For BeCl2, the polymer is propagated by intermolecular 3 2 electron interactions form chlorine lone pairs to (sp3 hybridised) Be. BeMe2 requires the formation of 3 centre/ 2 electron Be-C-Be bonds between the Be atoms and the methyl groups.
3H 3H 3H 3H 3H 3H

(c)

Apply Wades rules to predict the structure of the [B6H9]- anion. (5 marks)

Answer B6; n = 6 Electron count

B (6 x 3) = 18 H (9 x 1) = 9 Charge = 1 Total 28

Terminal B-H = 6 = 12 electrons Therefore, 28 12 = 16 available for skeletal bonding = 8 electron pairs = n + 2. Therefore nido structure based on 7 vertex pentagonal bipyramid .
H H BH BH H

HB BH

BH

B H

(d)

The covalent radius of sulfur is 1.03 . Provide an explanation for the S-S bond lengths in the following compounds; (a) S8 [2.06 ]; (b) H2S2 [2.06 ]; (c) [S4]2+ [1.98 ]. (5 marks)

Answer For both (a) and (b) S-S = double covalent bond length ie normal single bonds.
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C C eB

3H

C eB

3H

C C eB

3H

C C eB

3H

S
2+

S S

S42+ is planar and aromatic. assume sp2 hybridisation of S Valence electrons (6 x 4) = 24 - Four S-S bonds (4 x 2) = 8 - 4 x lone pairs = 8 - charge = +2

Residual electrons = 6 (ie 2n + 2, obeying Hckel rule) Can also be rationalised using Wades rules.

(e)

Poly(dialkysiloxanes) are versatile and chemically and thermally robust materials. Comment upon this statement with reference to the structures of this wide class of compounds. (5 marks)

Answer Short account of properties of siloxanes. Polymers propagated by SiOSi linkages. Extremely robust, both thermally and chemically, due to the strength of the SiC and C-H bonds as well as the strength of the SiOSi bonds (the mean SiO bond enthalpy is 466 kJmol-1). Synthesis by hydolysis of R2SiCl2.
H2O

nMe2SiCl2

-HCl

nMe2Si(OH)2

-H2O

(Me2SiO)n

Control of polymer chain length can be gained by addition of a chain-terminating group such as Me3SiCl and cross-linking can by hydrolysis in the presence of MeSiCl3.
Me

R3SiCl

H2O

Si Me

Me

Chain terminating group

Me

R2SiCl2

H2O

Si Me Me

Chain forming group

RSiCl3

H2O

Si O

Branching group

Hence, siloxane oils, elastomers (rubbers) or resins can be obtained most of which are of great technological use. May also mention that flexibility is maintatined at low temp due to lone pair electron density delocalisation from O into Si * (or d) orbitals.

2.I2 Transition Metal Chemistry

Answer BOTH part (a) AND part(b) Part (a). Answer EITHER i) OR ii) i) In recent years, carbenes of the type A shown below, have emerged as an important new class of ligands. Compare and contrast the sigma-donating and pi-accepting properties of these carbenes with amines NR3, phosphines PR3 and CO. How would you arrange these four types of ligands in the spectro-chemical series?
R N C N R

A (10 marks)

ANSWER: Carbenes are strong sigma-donors, but softer in character than amines, more comparable to PR3 (4 marks). Carbenes are poorer pi-acceptors than CO and PR3 (no accessible anti-bonding orbitals for back donation) (4 marks). In increasing o order: NR3 < CR2 < PR3 <CO. (2 marks)

ii) Depending on the ligand environment, iron(II) complexes can sometimes be in a spin crossover regime, which means that the high-spin and low-spin configurations are in an equilibrium. Determine the d-electron configuration and the magnetic moment spin-only value for both configurations. How will temperature affect the equilibrium. What will be the effect of raising the temperature be on the UV-vis spectrum? (10 marks) ANSWER: LS: t2g 6, eg* 0 0 unpaired electrons (so = 0 BM) (2 mark) HS: t2g 4, eg* 2 4 unpaired electrons (so = 4.9 BM) (2 mark) LS is favoured at lower termperature (larger CFSE) (3 marks) At higher temperature, HS is preferred, transitions become Laporte AND spin forbidden: d-d transitions become less intense. (3 marks)
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Part (b). Answer TWO of the following three questions: i) Find x,y and z in the following complexes by determining the oxidation state of the central metal from the experimental values of the effective magnetic moment eff. (NH4)x[Cr(H2O)2Br4] (NH4)y[MnCl4] (NH4)z[MnO4] eff = 4.87 BM eff = 5.90 BM eff = 1.61 BM (7.5 marks) ANSWER: Cr(II), d4HS, x = 2 (2.5 marks),Mn(II), d5, y = 2 (2.5 marks) and Mn(VI), z = 2 (2.5 marks) ii) The rate constants of replacement of Cl- by H2O in the following series of cationic platinum(II) complexes [PtClL(PEt3)2]+ is given below: L = pyridine: k = 810-2 s-1 L = 2-methyl pyridine: k = 210-4 s-1 L = 2,6-dimethyl pyridine: k = 110-6 s-1 Explain this observation. (7.5 marks) ANSWER: Pt(II) square planar. (1 mark) Substitutions are associative. (2 marks) Approach of incoming nucleophile H2O is slowed by steric protection of the axial site(s). (4.5 marks with picture) iii) Using an MO diagram, describe the metal-metal bonding in the following complexes and determine the bond order: a) [Cr2(CH3)8]4b) [Mo2(HPO4)4]2c) [Re2Cl4(PR3)4]+ (7.5 marks) ANSWER: Cr(II) d4, BO = 4 (2.5 marks); Mo(III) d3, BO = 3 (2.5 marks); Re(II)/Re(III) d5/d4, BO = 3.5 (2.5 marks).

2.I3 Molecular Orbitals in Inorganic Chemistry

a) Answer ALL parts of this question. (10 marks total) Construct the molecular orbital diagram for formaldehyde H2CO working in the axial system defined below. Diagrams must be clear. i) identify the molecular symmetry C2v (1 mark) ii) Construct the valence molecular orbital diagram for formaldehyde H2CO. Work in the axial system defined above. On your diagram identify the chemical fragments, draw all of the molecular orbitals and assign the symmetry labels.

a1

b1

1b1

b2

3a1

b1

b2

a1

1b2

b1

a1

mixing

b2 mixing

2a1

a1 a1

z z
O
O

a1
O

y x
H C H

y
H

C H H

C H

1-energy levels CH2 and O fragment and in complex 2-orbital pictures (note only central MOs required) 2-correct symmetry labels 1-discretionary (for example for placing the third a1 above b1) (6 marks) 6

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iv) orbital mixing between a1 orbitals, because they are the same symmetry and close in energy.

(3 marks) b) Answer ALL parts of this question. (total 15 marks) Consider an ozone molecule with three oxygen atoms arranged in an equilateral triangle, the point group is D3h
O O O

i) determine the reducible representation for the three p orbitals

the number of orbitals that don't move under the symmetry operations of the group:

D3h

E 3

2C3
0

3C 2
-1

h
-3

2S3 3 v
0 1

(1 mark) ii) write down the reduction and projection formulae, briefly explain each of the terms in both formulae reduction formula 1 nIR = k IR (Q) R (Q) h Q projection formula 1 P [ ] = IR (Q) Q [ ] h Q

nIR =number of times the irreducible representation IR contributes to the reducible representation R
h =number of operations in the point group
Q=a particular symmetry operation

k =the number of operations of Q in the point group

IR (Q ) =character of the irreducible representation (IR) under Q R (Q ) =the character of the reducible representation (R) under Q =waverfunction on which the projection operator acts
P [ ]=the molecular orbital wavefunction
(4 marks)
iii) use the reduction formula to determine the symmetry of the p based molecular orbitals, show your working. application of the reduction formula:
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R R R A A A 1 1 2 (E) (E) + 2 2 (C3 ) (C3 ) + 3 2 (C2 ) (C2 ) nA2 = 12 +1 A2 ( h ) R ( h ) + 2 A2 (S3 ) R (S3 ) + 3 A2 ( v ) R ( v )

nA2 = nA2 =

1 1 1 3 + 2 1 0 + 3 1 1 + 1 1 3 + 2 1 0 + 3 1 1 12 E C3 C2 h S3 v 1 12 [3 + 0 + 3 + 3 + 0 + 3] = = 1 12 12
R R R E E E 1 1 (E) (E) + 2 (C3 ) (C3 ) + 3 (C2 ) (C2 ) = 12 +1 E ( h ) R ( h ) + 2 E (S3 ) R (S3 ) + 3 E ( v ) R ( v )

nE

nE = nE =

1 1 2 3 + 2 1 0 + 3 0 1 + 1 2 3 + 2 1 0 + 3 0 1 12 E C3 C2 h S3 v 1 12 [6 + 0 + 0 + 6 + 0 + 0 ] = = 1 12 12
= A2 + E

(4 marks) iv) use the projection formula to determine the equation of the p based molecular orbitals, show your working. The molecular orbital wavefunctions do not need to be normalised.
p1 p3 C2 p2 C2
2C3 3C2 2 3 2S3 3 2 S3

D3h Q [p1 ]

E p1 1 p1

1 3

C2 -p1 -1 p1

C2 -p3 -1 p3

C2 -p2 -1 p2

h
-p1 -1 p1

1 3

p1 1 p1 p3 1 p3 p2 1 p2

p2 1 p2

p3 1 p3

-p2 -1 p2

-p3 -1 p3

A2

A2 (Q) Q [p1 ]

PA2 [p1 ]=

a
2

1 [p1 + p2 + p3 + p1 + p3 + p2 + p1 + p2 + p3 + p1 + p3 + p2 ] 12 1 1 = PA2 [p1 ]= [4 p1 + 4 p2 + 4 p3 ]= [p1 + p2 + p3 ] 12 3

2C3 3C2 2 S3 3 1 2 C3 C3

D3h Q [p1 ]

E p1 2

C2 -p1 0 0

C2 -p3 0 0

C2 -p2 0 0

h
-p1 -2 -2p1

1 2 S3 S 3

p1 0 0 p3 0 0 p2 0 0

p2 -1

p3 -1

-p2 1 -p2

-p3 1 -p3

E (Q) Q [p1 ]

2p1 -p2 -p3

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PE [p1 ]=

1 [2 p1 p2 p3 + 0 + 0 + 0 2 p1 p2 p3 + 0 + 0 + 0 ] 12 1 1 = PE [p1 ]= [4 p1 2 p2 2 p3 ]= [2 p1 p2 p3 ] 12 6

so e (1) =

1 1 [2 p1 p2 p3 ] now guess an orthogonal partner e (2) = 2 [p2 p3 ] 6 check that they are orthogonal:

E (1) E (2) = 0
2 p1 p2 p3 p2 p3 = 2 p1 p2 2 p1 p3 p2 p2 + p2 p3 p3 p2 + p3 p3
=0 =0 =1 =0 =0 =1

= 1 + 1 = 0

(5 marks) vi) draw an energy level diagram for the p based orbitals, draw the molecular orbital and write the associated equation beside each energy level, label the symmetry of each orbital.
e (1) =
1 [2 p1 p2 p3 ] 6

e (2) =

1 [p2 p3 ] 2 e

a2 =

1 [p1 + p2 + p3 ] 3
O O

a2

(2 marks)

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c) Answer ALL parts of this question. (total 15 marks) i) draw the full valence molecular orbital diagram for ML6 where M is a metal with d electrons and L are six sigma-bonding ligands. Label the symmetry of each set of energy levels.
t1u

a1g t1u eg a1g oct eg t 2 g t2 g eg t1u eg t1u a1g

L L L L L L L

a1g

L L

L M L L

1-energy levels M and L in right place 1-energy levels ML6 correctly determined 1-correct symmetry labels 1-discretionary (4 marks) ii) identify oct , the octahedral splitting parameter on your diagram. (see above) (1 mark) iii) draw an energy level diagram for the interaction of two trans -donor ligands L, with the d atomic orbitals of a metal M. Label the symmetry of each set of energy levels. Assume the molecule has D4 h symmetry and the axial system defined in the diagram below.
z
L L L L M L L

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b1g a1g eg b2 g eg b2 g eu eg
L L L L M L L

metal based

eg eu ligand based
L

1-energy levels M and L in right place 1-energy levels M-L correctly determined 1.5-correct symmetry labels 1-discretionary (4.5 marks) iv) Identify the molecular orbitals primarily associated with the metal, and those primarily associated with the ligand. (see above) (1 mark) v) Draw the molecular orbitals that involve metal d atomic orbital and L fragment orbital interactions. Label the d atomic orbitals in each diagram.
z eg (d xz ) x
M

z eg (d yz )

z eg (d xz ) x y ligand based

z eg (d yz )

y metal based

1-putting dAOs and p orbitals down 1-coefficients right (larger dAO on metal orbitals, larger L on ligand orbitals) 1-making d based MOs antibonding and L based MOs bonding 1-correct dAO labels for the axial system 0.5 discretionary (4.5 marks)

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