Course UC-204

Mid Term 1 (Date : 24.02.2023)

Total Marks : 25

2-Marks Questions: (2 x 5 = 10)

1. The IR (Infrared) spectra of 2-prapanol exhibits characteristic broad absorption at 3500 cm¯1
assigned to the ν(OH) mode. Whereas the dilute solution of the same shows a shift to higher stretching
frequency at ~3600 cm¯1. Reason out the shift in the frequency and the broadness of the spectrum.

Hydrogen bonding is readily detected by the shift to lower wavenumber and broadening of E_H
stretching bands in infrared spectra and by unusual proton chemical shifts in proton NMR.
The IR spectrum of a hydrate, alcohol or carboxylic acid exhibits a characteristic absorption around
3500 cm1 assigned to the (OH) mode (see Figure 4.13). The typical broadness of this band can be
explained in terms of the involvement of the OH hydrogen atom in hydrogen bonding. In cases where
we can compare the stretching frequencies of the same molecule with and without hydrogenbonded
association (e.g. liquid water and water vapour), a shift is observed to higher wavenumber as
hydrogen bonding is lost. Similar observations are noted for other hydrogen bonded systems.

2. The reactivity and solubility of alkyllithium is enhanced by adding a chelating ligand such as
tetramethyl ethylenediamine (TMEDA), Why? Explain with an example.

The reactivity and solubility of alkyllithium is enhanced by adding a chelating ligand such as
tetramethylethylenediamine, TMEDA (8), which breaks up any tetramers to give complexes such as
[BuLi(TMEDA)]2.

3. Explain the nature of Be(OH)2 and Mg(OH)2.

Be(OH)2 and Al(OH)3 are amphoteric, reacting with both acids and bases (see equations 12.24 and 12.25 for reactions
of Be(OH)2, and equations 7.41 and 7.42 for Al(OH)3); the hydroxides of the later group 2 metals are basic.
Beryllium hydroxide is amphoteric and this sets it apart from the hydroxides of the other group 2 metals which are
basic. In the presence of excess [OH], Be(OH)2 behaves as a Lewis acid (equation 12.24), forming the tetrahedral
complex ion 12.7, but Be(OH)2 also reacts with acids, e.g. reaction 12.25.
4. Suggest the possible structure of BeCl2 in solid and vapor phase.

The structure of solid BeCl2 is a polymeric chain (1). The local structure is an almost regular
tetrahedron around the Be atom and the bonding can be considered to be based on sp3
hybridization. In BeCl2 the chloride ion has sufficient electron density for 2c,2e covalent bonding to
take place. Beryllium chloride is a Lewis acid, readily forming adducts with electron-pair donors such
as diethyl ether (2). In the vapour phase the compound tends to form a dimer based on sp2
hydridization (3), and when the temperature is above 900.C linear monomers are formed, indicating
sp hybridization (4).

5. Write the reaction of B2H6 with NMe3 and NH3

Soft and bulky Lewis bases cleave diborane symmetrically; more compact and hard Lewis bases cleave
the hydrogen bridge unsymmetrically; although it reacts with many hard Lewis bases, diborane is best
regarded as a soft Lewis acid.

Two different cleavage patterns have been observed, namely symmetric cleavage and unsymmetric
cleavage. In symmetric cleavage, B2H6 is broken symmetrically into two BH3 fragments, each of which
forms a complex with a Lewis base:

The direct reaction of diborane and ammonia results in unsymmetrical cleavage, which is cleavage
leading to an ionic product:
3-Marks Questions: (3 x 5 = 15)

1. Explain the heterolytic cleavage of hydrogen with example.

Heterolytic dissociation of H2 depends on a metal ion (for hydride coordination) and a Brønsted base
being in close proximity. Reaction of H2 with a ZnO surface appears to produce a Zn(II)-bound hydride
and an O-bound proton. This reaction is involved in the production of methanol by catalytic
hydrogenation of carbon monoxide over Cu/ZnO/Al2O3.

CO(g) 2H2(g) → CH3OH(g)

Another example in which H2 is dissociated into a hydride and a proton is during its oxidation at the
active site of metalloenzymes known as hydrogenases

Heterolytic dissociation into H and Hions induced by adsorption on a heteroatom surface, such as a
metal oxide:

2. Give the reason for the blue color solution of sodium in Liq. NH3 (write the equation). Provide
an example for the application of this solution.

Sodium dissolves in pure, anhydrous liquid ammonia (without hydrogen evolution) to give solutions that are deep
blue when dilute. The colour of these metal–ammonia solutions originates from the tail of a strong absorption band
that peaks in the near infrared.1 The dissolution of sodium in liquid ammonia to give a very dilute solution is
represented by the equation
Na(s) Na+ (am) + e (am)
These solutions survive for long periods at the temperature of boiling ammonia (_33_C) and in the absence of air.
However, they are only metastable and their decomposition is catalysed by some d-block compounds:

Concentrated metal_ammonia solutions have a metallic bronze colour and have electrical conductance close to that
of a metal. These solutions have been described as ‘expanded metals’ in which e_(am) associates with the
ammoniated cation. This description is supported by the fact that, in saturated solutions, the ammonia-to-metal
ratio is between 5 and 10, which corresponds to a reasonable coordination number for the metal.
The blue metal_ammonia solutions are excellent reducing agents. For example, the Ni(I) complex [Ni2(CN)6]4_, in
which nickel is in an unusually low oxidation state, Ni(I), may be prepared by the reduction of Ni(II) with potassium in
liquid ammonia:

3. Draw the structure of Berrylocene Be(C5H5)2 in the solid state. The 1H NMR spectra of beryllocene
at -135 °C shows only one signal, explain why?
An interesting organoberyllium compound is beryllocene, (C5H5)2Be, which, although the formula
suggests an analogy with ferrocene (Section 22.19), in fact has a different structure in the crystalline
state, with the Be atom positioned directly above the centre of one cyclopentadienyl ring and below
a single C atom on the other ring (11). However, the low-temperature (–135ºC) NMR spectrum of this
compound in solution suggests that the two rings are equivalent, indicating that even at this low
temperature the Be atom and the C5H5 rings are rearranging rapidly.

4. Describe the bonding in a) BF3, b) AlCl3, c) B2H6

BF3, monomer with back bonding.

AlCl3-dimer structure

B2H6- banana bond

5. The [P3I6]+ ion is formed in the reaction of P2I4 with PI3 and Ag[Al{OC(CF3)3}4].CH2Cl2. The solution
31P NMR spectrum shows a triplet and a doublet with relative integrals 1:2 (J = 385 Hz). Suggest a
structure for [P3I6]+ that is consistent with the NMR spectroscopic data.