CHEMISTRY OF MAIN GROUP ELEMENTS

CH3101
ASSIGNMENT

Swaraj Biswas
15MS030
IISER-Kolkata
 CHEMISTRY OF MAIN GROUP ELEMENTS

Contents

Title Page no.

1. Organolithium
Compounds……………………………………………………………………. 1-3
2. Boron
Halides………………………………………………………………………………………
… 3-6
3. Carboranes…………………………………………………………………………………
…………. 6-7
4. Group 13
hydrides…………………………………………………………………………………. 8
5. Carbon Nitrogen
Compounds………………………………………………………………… 9-10
6. Carbon
Halides……………………………………………………………………………………….
10-15
7. Hydrazine, Hydroxyl amine,
Azides…………………………..……………………………. 15-16
8. Oxides of
nitrogen…………………………………………………………………………………
19-21
9. Phosphazenes……………………………………………………………………………
…………. 27
10. Halides of
Phosphorus………………………………………………………………………….. 24-
26

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1. ORGANOLITHIUM COMPOUNDS:

The organolithium compounds, characterized by a C-Li bond are important in organic synthesis as R-Mg-
X. Li is less electronegative than carbon, and C-Li bond is polarized as in organo-magnesium halides. The
organolithium compounds are more reactive compared to organo-magnesium compounds and are
expected to behave both as a nucleophile and a base.
Alkyllithium compounds are widely used as very strong bases, nucleophiles and reagents for metallations
in organic synthesis. The following table shows, that alkanes and arenes are very weak acids, hence their
corresponding lithium-derivatives are extremely strong bases.

The most common members of the alkyllithiumfamily are n-butyllithium, methyllithium and tert-
butyllithium (for which 2-methylpropane is the corresponding acid).
Although simple alkyllithium species are often represented as monomer RLi, they exist as aggregates
(oligomers) or polymers. Their structures depend on the nature of organic substituent and the presence of
other ligands. These structures have been elucidated by a variety of methods, notably 6Li, 7Li,
and 13C NMR spectroscopy and X-ray diffraction analysis. Computational chemistry supports these
assignments.
The relative electronegativities of carbon and lithium suggests that the C-Li bond will be highly polar.
However, certain organolithium compounds possess properties such as solubility in nonpolar solvents that
complicate the issue. While most data suggest the C-Li bond to be essentially ionic, there has been debate
as to whether a small covalent character exists in the C-Li bond.
In allyl lithium compounds, the lithium cation coordinates to the face of the carbon π bond in an η-
3 fashion instead of a localized, carbanionic center, thus, allyllithiums are often less aggregated than

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alkyllithiums. In aryllithium complexes, the lithium cation coordinates to a single carbanion center
through a Li-C σ type bond.
1

Reactions of Organolithium compounds:

TRANSMETALLATION

The organolithium compounds are very often used to prepare other metallorganic compounds through
the transmetallation reaction:

R-Li + M-X R-M + Li-X

(M = Metalion, X = Halide)

This reaction has been used to prepare the important organo-copper(A) and organo-titanium (B) and
many other metallorganic compounds46 which have often higher selectivity than the organolithium
compounds.

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(A) 2 R-Li + CuX[R-Cu + R-Li + LiX] R2CuLi + LiX

(B) R-Li + TiCl4 R-TiCl3 + LiCl

Highly functionalized mixed cuprates have been synthesized recently by halogen-metal exchange of
sterically hindered alkylhalogenides with tert-butyllithium and subsequent transmetallation to the
cuprate followed by a second halogen-metal-exchange.

2. BORON HALIDES:

Boron forms trihalides compounds with all the halide members and the trihalides are mostly monomeric
and trigonal planner molecules. Back-donation of nonbonding electrons on halogen atoms into the empty
pz orbital of boron gives the B-X bonds partial double bond nature and is also responsible for the stability
of monomers. All boron halides are Lewis acid and the order of Lewis acidity is BI3 > BBr3> BCl3> BF3.
Except BF3 all the halides get hydrolysed rapidly in water. BI3 reacts explosively with water. BCl3 and
BBr3 are volatile liquids while the triiodide is unstable white solid at room temperature. BF 3 is a
colourless gas at room temperature.
BF3 is prepared via treatment of B2O3 with CaF2 in H2SO4. BF3 on reaction with Al2Cl6 and Al2Br6 gives
BCl3 and BBr3, respectively. Boron trifluoride, being a Lewis acid forms adducts with various electron
pair donor species. A very common example is BF3·OEt2. With water, below 200C BF3 forms BF3·H2O
and BF3·2H2O. In dilute condition BF3 produces tetrafluoroborate ion with water. The solution is known
as fluoroiboric acid.
4BF3 + 6H2O 3H3O+ + 3BF4- + B(OH)3
Though the acid cannot be isolated, it forms various salts and solvates, e.g., NaBF4, NH4BF4, HBF4·Et2O.
BF4- is isoelectronic to CF4 andhas a similar tetrahedral geometry.
Other trihalides also forms BX4- , though they need larger cations to stabilize themselves.
Mixing of any two of BF3, BCL3, BBr3causes rapid exchange of halogens and forms mixed-halide species
like BFCl2, BF2Cl etc.
For it’s excellent Lewis acid nature BF3 is widely used in organic Synthesis. A number of reactions like
conversion of alcohol and acids to esters, polymerization of olefin and olefin oxides and Fidelcraft type
alkylation and acetylation reactions are performed in presence of BF3.
Boron trifluoride on reaction with NaBH4 in ether produces B2H6.
3

Lewis Acidity of Boron Halides

All three lighter boron trihalides, BX3 (X = F, Cl, Br), form stable adducts with common Lewis bases.
Their relative Lewis acidities can be evaluated in terms of the relative exothermicities of the adduct-

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forming reaction. Such measurements have revealed the following sequence for the Lewis acidity:
BF3 < BCl3 < BBr3 (in other words, BBr3 is the strongest Lewis acid).
This trend is commonly attributed to the degree of π-bonding in the planar boron trihalide that would be
lost upon pyramidalization (the conversion of the trigonal planar geometry to a tetrahedral one) of the
BX3 molecule, which follows this trend: BF3 > BCl3 > BBr3 (that is, BBr3 is the most easily
pyramidalized). The criteria for evaluating the relative strength of π-bonding are not clear, however. One
suggestion is that the F atom is small compared to the larger Cl and Br atoms, and the lone pair electron
in the 2pz orbital of F is readily and easily donated, and overlaps with the empty 2pz orbital of boron. As
a result, the π donation of F is greater than that of Cl or Br. In an alternative explanation, the low Lewis
acidity for BF3 is attributed to the relative weakness of the bond in the adducts F3B-L.

Boron trifluoride

Boron (III) trifluoride structure, BF3, showing the "empty" boron p orbital in pi-type coordinate covalent
bonds.

Boron Tribromide

Boron tribromide (BBr3) is a colorless, fuming liquid compound that contains boron and bromine. The
reaction of boron carbide with bromine at temperatures above 300 °C leads to the formation of boron
tribromide. The product can be purified by vacuum distillation.
BBr3 is decomposed by water and alcohols. It is an excellent demethylating or dealkylating agent for the
cleavage of ethers, also with subsequent cyclization (formation of cyclic molecules), often in the
production of pharmaceuticals. The mechanism of ether dealkylation proceeds via the formation of a
complex between the boron center and the ether oxygen followed by the elimination of an alkyl bromide
to yield a dibromo(organo)borane. The dibromo(organo)borane can then undergo hydrolysis to give a
hydroxyl group, boric acid, and hydrogen bromide as products. The electronics industry uses boron
tribromide as a boron source in pre-deposition processes for doping in the manufacture
of semiconductors.
4

Boron Trichloride:

Boron trichloride (BCl3) is a colorless gas that is a valuable reagent in organic synthesis, but is also
dangerously reactive. Boron trichloride is produced industrially by direct chlorination of boron oxide and
carbon at 500 °C. The synthesis is analogous to the Kroll process for the conversion of titanium dioxide to
titanium tetrachloride. In the laboratory, BF3 reacts with AlCl3 to create BCl3 via halogen exchange.
Boron trichloride does not form dimers, although there is some evidence that may indicate dimerization at
very low temperatures (20 K). NMR studies of mixtures of boron trihalides shows the presence of mixed

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halides, which may indicate a four center intermediate (that is, a dimer). The absence of dimerization
contrasts with the other trihalides of group 13, which contain four or six coordinate metal centers.
Boron trichloride is a starting material for the production of elemental boron. It is also used in
the refining of aluminium, magnesium, zinc, and copper alloys to remove nitrides, carbides, and oxides
from molten metal. It has been used as a soldering flux for alloys of aluminium, iron, zinc, tungsten, and
monel. Aluminum castings can be improved by treating the melt with boron trichloride vapors.

Boron Trifluoride

Boron trifluoride (BF3) is a pungent, colorless, toxic gas that forms white fumes in moist air. The
molecule is isoelectronic with the carbonate anion, CO32−. BF3 is commonly referred to as "electron
deficient" because of its exothermic reactivity toward Lewis bases. BF3 is manufactured by the reaction of
boron oxides with hydrogen fluoride. Since boron trifluoride is corrosive, the metals suitable for handling
boron trifluoride include stainless steel, monel, and hastelloy. In the presence of moisture, boron
trifluoride corrodes stainless steel. Polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene
fluoride, and polypropylene show satisfactory resistance.

Subhalides:

Boron also forms B2X4 type compounds. They have two BX2 unites connected via B-B bonds and are
called as boron subhalides.In liquid and gaseous state they are not planner , the two BX 2 unites stays
perpendicular to each other.In polyhedral boron halides B:X ratio is 1:1 and they resemblescloso
structure. BnXn species are generally neutral and stable. As they only have n framework electron PSEPT
rules are not applicable to them.
5

3. CARBORANES:
One of the famous cluster family of boron is carboranes, characterised by presence of one or more carbon
in a borane cluster framework. Mostly these species contains two carbon atoms per cage but up to 5
carbon-carboranes are known to exist. The Carboranes form a class of nonclassical molecules in which
cage carbons participates in delocalized bonding and shows abnormal coordination of 5 and 6.
Closo-carboranes: C2Bn-2Hn and CBn-1Hn- are isoelectronic analogues of BnHn2- dianions. Each of the n
vertex carboranes has the same geometry as their borane counterpart.With contribution of 3 electrons
from each C-H unit and 2 electrons from each B-H unit gives rise to (n+1) electron pairs favouring closo
structure. The closo carboranes are highly tolerant to thermal and oxidative decompositions due to
extensive delocalisation of skeletal electrons. The C2B10H12 compounds, harbouring 26 skeletal electrons
are 3D analogues of benzene and known as ‘superaromatics’. The C2B10H12isomers are white non-volatile
solid while lower members are volatile liquids. Carboranes can be prepared by various ways. Small
carboranes are formed via high energy combination of boranes and alkynes in electric discharge or flash
reactions. They can be prepared from alkyl-boranes as well. The bigger carborens such as C2B10H12are

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produced in reaction of B10H12L2 Lewis base adduct with alkynes. Carboranes containing functional
groups can be obtained by electrophilic substitution on the parent compounds.

Structural outline of carboranes and their

borane counterparts.
From: Advanced Inorganic Chemistry Cotton Wilkinson

The C2B10H12cluster is used in the synthesis of exceptionally stable polymers due to it’s thermal stability
and ‘electron sink’ nature. Organ substituted derivatives of the above cluster is in clinical trials of BNCT
treatment of brain tumours.
Isomers and Polyhedral Rearrangements: Closo carboranes can undergo thermal isomerisation by
intramolecular rearrangement. The major driving force is the separation of relatively positive carbon
centres and it leads to stabilization of isomers with highest C-C separation. Among ortho(1,2), meta(1,7)
and para(1,12) C2B10H12 the last one is most stable and is probably the most stable covalent neutral
molecule known with thermal stability extending well over 7000C. CH acid strength decreases with
6
increase in C-C separation.Though the exact mechanism of such intramolecular rearrangement is not
known, according to Lipscomb the isomerisation goes through ‘diamond-squre-diamond’ process
involving a cubooctahedral intermediate.
Nidoand Arachno carboranes:These carboranes have an open-cage geometry and forms much larger and
structurally far more diverse group than closo carboranes. Due to their open cage structure the nido and
archno carboranes and their deprotonated anions are quite reactive and involve in sandwich-binding of
metals.

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4. GROUP 13 HYDRIDES:

Group 13 elements Al, Ga forms Hydride. AlH3 is prepared by reaction between LiAlH 4 and H2SO4.
2LiAlH 4 + H2SO4 2AlH3 + 2H2 + Li2SO4
Gallium hydride is prepared via halide exchange:
Ga2CL6 + 4Me3SiH [H2GaCl]2 + 4Me3SiCl,[H2GaCl]2 + 2LiGaH4 [GaH3]2
AlH3 is polymeric, more reactive than boranes, isostructural with AlF3 and Forms 3D lattice. Gallane is a
molecular compound with structural similarities with borane. It is volatile and thermally and
hydrolytically unstable. Both Al and Ga forms mixed hydride with boranes producing HM{(µ-H)2BH 2}2
(M= Al,Ga) and Al{(µ-H)2BH2}3. Al and Ga hydrides are used as precursor to metal filma and III-IV
semiconductors.
Hydride anions of these metals are formed by the following reaction:
4LiH + MCl3 LiMH4 + 3LiCl.
LiAlH4 is used in organic reactions as a source of H-. it is a non-volatile crystalline solid. It reacts water
explosively to give H2 gas. It is soluble in ethers and can be solubilized in benzene with aid of crown
ethers.
Like borane these hydrides also show Lewis acid nature and forms donor adducts.
8

5. CARBON NITROGEN COMPOUNDS:

Small inorganic carbon - nitrogen compounds are cyanogen, hydrogen cyanide, cyanamide, isocyanic
acid and cyanogen chloride.

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Molar Boiling Melting

composition
mass (g/mole) point °C point °C

cyanogen (CN)2 52.03 -21 -28

hydrogen cyanide HCN 27.03 25-26 -12 - -14

260
cyanamide CN2H2 42.04 44
(decomp.)

isocyanic acid HNCO 43.03 23.5 -86

cyanogen chloride CNCl 61.47 13 -6

chlorosulfonyl
CNClO3S 141.53 107 -44
isocyanate

cyanuric chloride (NCCl)3 184.41 192 154

Inorganic carbon-nitrogen compounds

Outside organic chemistry the important species of C-N pair are cyanide, cyanate and thiocyanate iopn
and their derivatives.
The first Member is cyanogen (C2N2), also known as pseudo-halogen. It has three isomeric structure:
N=C-C=N, C=N-C=N and C=N-N=N. It is linear. Cyanogen can be prepared by oxidation of HCN by
NO2 over Calcium oxide glass. On dissociation it gives CN radicals however in basic solution
disproportionation dissociation is observed which is similar to halogens. Stoichiometric mixture of O2
and C2N2on burning produces one of the hottest flames (~5050K). Impure cyanogen on heating gives
paracyanogen polymer (stable up to 8500C). KCN and ICN reacts to form linear polycyanogen

Paracyanogen
From: Advanced Inorganic Chemistry Cotton Wilkinson

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Paracyanogen is the polymerization product of cyanogen. Cyanuric chloride is the trimer of cyanogen
chloride and 2-cyanoguanidine is the dimer of cyanamide.
Other types of inorganic compounds include the inorganic salts and complexes of the carbon-
containing cyanide, cyanate, fulminate, thiocyanate and cyanamide ions. Examples of cyanides are copper
cyanide (CuCN) and potassium cyanide (KCN), examples of cyanates are potassium cyanate (KNCO)
and silver cyanate (AgNCO), examples of fulminates are silver fulminate (AgOCN) and mercury
fulminate (HgOCN) and an example of a thiocyanate is potassium thiocyanate (KSCN).
HCN: HCN is a covalent weak acid with Pk= 9.0. in aqueous solution. In gaseous state it colourless and
extremely toxic. HCN condenses at 25.60C and the liquid is very unstable and undergo polymerisation.
HCN is thought to have been one of the small molecule in earth’s primitive atmosphere and had played a
important role in origin of biological systems aka life.HCN is used to synthesize Methylmethacrylate and
nylon. Waste HCN is oxidised to give oximide, a component for fertilizers.

6. CARBON HALIDES:

Any of the compounds of carbon with the halogens is termed as carbon halides . Carbon halides are
usually regarded asderivatives of hydrocarbons, in which hydrogen has been wholly replaced by a
halogen.
The simplest carbon halides are tetrahalides of the general formula CX 4. These compounds have a
tetrahedral structure, with the C-F, C-Cl, C-Br, and C-I bond lengths equal to, 1.36, 1.76, 1.94, and
2.12 angstroms and bond energies equal to, respectively, 487,340,285 and 214 KJ per mole. Under
ordinary conditions, CF4 is a gas with a boiling point of -128°C; CCl 4 is a liquid with a melting point of -
22.9° C and a boiling point of 76.8° C CBr4 and CI4 are solids with melting points of 93.7°C and
171°C, respectively. All the tetrahalides, virtually insoluble inwater, are soluble in organic solvents.

10
The stability of CX4 compounds decreases with decreasing bond energy, and the chemicalreactivity
increases in moving from fluorine to iodine. The compounds CF4 and CC14 arestable when heated and
when exposed to air, light, or acids. CI4 readily decomposes uponheating. Only CF4 can be obtained by
a direct reaction of its constituent elements. One of themethods for the synthesis of CC1 4 and CBr4 is
the reaction of CS2 with the correspondinghalogens. CI4 is obtained from the reaction of CC14 with the
iodides of aluminum, bismuth, and other metals.
Carbon tetrachloride has the greatest importance among the carbon tetrahalides. Mixedcarbon halides are
also known, for example, CC1F3, CBr2Cl2, and C2Br2F4. Many carbonhalides are widely used in various i
ndustries. For example, difluorodi-chloromethane (CC12F2) and trichlorofluoromethane (CC13F) are
used ascoolants in refrigerators (Freons);tetrafluoroethylene (C2F4) and trifluorochloroethylene (C2C1F3)

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are used as monomers in theproduction of fluoroplastics; hexachloroethane (C2CI6) serves as a camphor s

ubstitute; andcertain carbon halides containing fluorine and chlorine are components of synthetic oils.

The carbon-halogen bonds (apart from the carbon-iodine bond) are polar, because the electron pair is
pulled closer to the halogen atom than the carbon. This is because (apart from iodine) the halogens are
more electronegative than carbon. The electronegativity values are: C – 2.5, F – 4.0, Cl – 3.0, Br – 2.8,
I – 2.5.
This means that in addition to the dispersion forces there will be forces
due to the attractions between the permanent dipoles (except in the iodide case). The size of those dipole-
dipole attractions will fall as the bonds get less polar (as you go from chloride to bromide to iodide, for
example). Nevertheless, the boiling points rise! This shows that the effect of the permanent dipole-dipole
attractions is much less important than that of the temporary dipoles which cause the dispersion forces.
The large increase in number of electrons by the time you get to the iodide completely outweighs the loss
of any permanent dipoles in the molecules.

CLASSES OF HALIDES:

12
Notice that bond strength falls as you go from C-F to C-I, and notice how much stronger the carbon-
fluorine bond is than the rest. To react with the alkyl halides, the carbon-halogen bond has got to be
broken. Because that gets easier as you go from fluoride to chloride to bromide to iodide, the compounds
get more reactive in that order. Iodoalkanes are the most reactive and fluoroalkanes are the least. In fact,
fluoroalkanes are so unreactive that we shall pretty well ignore them completely from now on in this
section!
The electronegativities of carbon and iodine are equal and so there will be no separation of charge on the
bond.One of the important set of reactions of alkyl halides involves replacing the halogen by something
else - substitution reactions. These reactions involve either:

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 the carbon-halogen bond breaking to give positive and negative ions. The ion with the positively
charged carbon atom then reacts with something either fully or slightly negatively charged.
 something either fully or negatively charged attracted to the slightly positive carbon atom and
pushing off the halogen atom.
we might have thought that either of these would be more effective in the case of the carbon-fluorine
bond with the quite large amounts of positive and negative charge already present. But that's not so - quite
the opposite is true! The thing that governs the reactivity is the strength of the bonds which have to be
broken. If is difficult to break a carbon-fluorine bond, but easy to break a carbon-iodine one.

7. HYDRAZINE:

Hydrazine is an inorganic compound with the chemical formula N2H4 (also written H2NNH2). A
simple pnictogen hydride, it is a colorless flammable liquid with an ammonia-like odor. Hydrazine is
highly toxic and dangerously unstable unless handled in solution. As of 2000, approximately 120,000 tons
of hydrazine hydrate (corresponding to a 64% solution of hydrazine in water by weight) were
manufactured worldwide per year. Hydrazine is mainly used as a foaming agent in
preparing polymer foams, but significant applications also include its uses as
a precursor to polymerization catalysts and pharmaceuticals. Additionally, hydrazine is used in
various rocket fuels and to prepare the gas precursors used in air bags. Hydrazine is used within both
nuclear and conventional electrical power plant steam cycles as an oxygen scavenger to control
concentrations of dissolved oxygen in an effort to reduce corrosion.

Hydrazine
derivatives

15

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HYDRAZINE
HYDRATES
AND
HYDRAZINE
HALIDES

8 . H Y D R O X Y L A M I N ES :

Hydroxylamine is an inorganic compound with the formula NH2OH. The pure material is a white,
unstable crystalline, hygroscopic compound. However, hydroxylamine is almost always provided and
used as an aqueous solution. It is used to prepare oximes, an important functional group. It is also an
intermediate in biological nitrification. In biological nitrification, the oxidation of NH3 to hydroxylamine
is mediated by the enzyme ammonia monooxygenase (AMO). Hydroxylamine oxidoreductase (HAO)
further oxidizes hydroxylamine to nitrite.

16

PREPARATION:

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NH2OH can be produced via several routes.

Raschig process: Aqueous ammonium nitrite is reduced by HSO3− and SO2 at 0 °C to yield a
hydroxylamido-N,N-disulfonate anion: NH4NO2 + 2 SO2 + NH3 + H2O → 2 NH4+ + N(OH)(OSO2)22−
This anion is then hydrolyzed to give (NH3OH)2SO4:
N(OH)(OSO2)22− + H2O → NH(OH)(OSO2)− + HSO4−
2 NH(OH)(OSO2)− + 2 H2O → (NH3OH)2SO4 + SO42-
Solid NH2OH can be collected by treatment with liquid ammonia. Ammonium sulfate, (NH4)2SO4, a
side-product insoluble in liquid ammonia, is removed by filtration; the liquid ammonia is evaporated to
give the desired product.
The net reaction is:
2NO2- + 4SO2 + 6H2O + 6NH3 → 4SO42− + 6NH4+ + 2NH2OH
Hydroxylammonium salts can then be converted to hydroxylamine by neutralization:
(NH3OH)Cl + NaOBu → NH2OH + NaCl + BuOH

REACTIONS:
A. Hydroxylamine reacts with electrophiles, such as alkylating agents, which can
attach to either the oxygen or the nitrogen atoms:

R-X + NH2OH → R-ONH2 + HX

R-X + NH2OH → R-NHOH + HX

B. The reaction of NH2OH with an aldehyde or ketone produces an oxime.

R2C=O + NH2OH∙HCl , NaOH → R2C=NOH + NaCl + H2O

This reaction is useful in the purification of ketones and aldehydes: if

hydroxylamine is added to an aldehyde or ketone in solution, an oxime forms,
which generally precipitates from solution; heating the precipitate with an
inorganic acid then restores the original aldehyde or ketone.
17

C. Hydroxylamine explodes with heat:

4 NH2OH + O2 → 2 N2 + 6 H2O

9. AZIDES:

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Azide is the anion with the formula N3−. It is the conjugate base of hydrazoic acid (HN 3). N3−
is a linear anion that is isoelectronic with CO2, NCO−, N2O, NO2+ and NCF. Per valence bond
theory, azide can be described by several resonance structures. Azide is also a functional
group in organic chemistry, RN3. The dominant application of azides is as a propellant in air bags.

An Azide reaction shown below

Importance:
Because of the hazards associated with their use, few azides are used commercially although they
exhibit interesting reactivity for researchers. Low molecular weight azides especially are
considered hazardous and are avoided. In the research laboratory, azides are precursors to amines. They
are also popular for their participation in the and in Staudinger ligation. These two reactions are generally
quite reliable, lending themselves to combinatorial chemistry.The antiviral drug zidovudine (AZT)
contains an azido group. Some azides are valuable as bioorthogonal chemical reporters.

OXIDES OF N2:
Nitrogen oxide may refer to a binary compound of oxygen and nitrogen, or a mixture of such compounds:
Nitric oxide, also known as nitrogen monoxide (NO), nitrogen(II) oxide
Nitrogen dioxide (NO2), nitrogen(IV) oxide
Nitrous oxide (N2O), nitrogen(−I,III) oxide
Nitrosylazide (N4O), nitrogen(−I,0,I,II) oxide
Oxatetrazole (N4O)
Dinitrogen trioxide (N2O3), nitrogen(II,IV) oxide
Dinitrogen tetroxide (N2O4), nitrogen(IV) oxide
Dinitrogen pentoxide (N2O5), nitrogen(V) oxide
Trinitramide (N(NO2)3 or N4O6), nitrogen(0,IV) oxide
Nitrite (NO2-)Nitrate (NO3-)Nitronium knoojsi (NO2Nitrosonium (NO+)
peroxonitrite (ONO−2)
The compounds NO and NO2 are radicals. In addition, there are several anions of nitrogen oxides. The
most stable of these is the nitrate anion: Nitrate (NO3−), trioxonitrate(V) ion but other
nitrogen oxoanions include nitrite, peroxonitrite, trioxodinitrate (hyponitrate), and nitroxylate.
In atmospheric chemistry, air pollution, and related fields, nitrogen oxides refers specifically to NOx (NO
and NO2). Only the first three of these compounds can be isolated at room temperature. N2O3, N2O4, and
N2O5 all decompose rapidly at room temperature. NO3, N4O, and N(NO2)3 are very reactive. N2O is stable
and rather unreactive at room temperature, while NO and NO2 are quite reactive but nevertheless quite
stable when isolated.

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NOX

NOx (often written NOx) refers to NO and NO2. They are produced during combustion, especially at high
temperature. These two chemicals are important trace species in Earth's atmosphere. In the troposphere,
during daylight, NO reacts with partly oxidised organic species (or the peroxy radical) to form NO2,
which is then photolysed by sunlight to reform NO:
19
NO + CH3O2 → NO2 + CH3O
NO2 + sunlight → NO + O
The oxygen atom formed in the second reaction then goes on to form ozone; this series of reactions is the
main source of tropospheric ozone. CH3O2 is just one example of many partly oxidised organic molecules
that can react with NO to form NO2.These reactions are rather fast, so NO and NO2 tend to cycle, but the
sum of their concentration ([NO] + [NO2]) tends to remain fairly constant. Because of this cycling, it is
convenient to think of the two chemicals as a group; hence the term NOx.
In addition to acting as a main precursor for tropospheric ozone, NOx is also harmful to human health in
its own right.NOx may react with water to make nitric acid, which may end up in the soil, where it
makes nitrate, which is of use to growing plants.

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9. PHOSPHAZENES:

Phosphazenes are a class of chemical compounds in which a phosphorus atom is covalently linked to
a nitrogen atom by a double bond and to three other atoms or radicals by single bonds. While other
substitutions produce relatively persistent compounds, in organic synthesis the term largely refers to
species with three amino substituents bound to phosphorus. The compounds are unusually stable
examples of the phosphorane class of molecules and have a remarkable proton affinity. As such, they are
one of the eminent examples of neutral, organic superbases

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.
Phosphazene bases are established reagents in organic synthesis. Perhaps the best known phosphazene
bases are BEMP with an acetonitrile pKa of the conjugate acid of 27.6 and the phosphorimidic triamide t-
Bu-P4 (pKBH+ = 42.7) also known as Schwesinger base after one of its inventors.

Polyphosphazenes

Polyphosphazenes include a wide range of hybrid inorganic-organic polymers with a number of

different skeletal architectures that contain alternating phosphorus and nitrogen atoms. Nearly all of
these molecules contain two organic or organometallic side groups attached to each phosphorus atom.
These include linear polymers with the formula (N=PR1R2)n, where R1 and R2 are organic or
organometallic side groups. The linear polymers are the largest group, with the general structure shown
schematically in the picture. Other known architectures are cyclolinear and cyclomatrix polymers in
which small phosphazene rings are connected together by organic chain units. Other architectures are
available, such as block copolymer, star, dendritic, or comb-type structures. More than 700 different
polyphosphazenes are known, with different side groups (R) and different molecular architectures.

10. HALIDES OF PHOSPHORUS:

Phosphorous trihalides, PX3, are produced from the direct reaction of phosphorous with the
appropriate halogen, The fluoride is readily made from the halide exchange reaction of PCl 3 with
fluoride salts. Mixed trihalides are formed by halide exchange,

A summary of the physical properties of the phosphorous trihalides is given in. All the
compounds have a pyramidal structure in the vapor phase and in solution.

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Selected physical properties of the phosphorous trihalides.

Compound Mp (°C) Bp (°C) P-X (Å) X-P-X (°)

PF3 -151.5 -101.8 1.56 96.3

PCl3 -93.6 76.1 2.04 100

PBr3 -41.5 173.2 2.22 101

PI3 61.2 200 (dec.) 2.43 102

The phosphorous trihalides hydrolyze to phosphoric acid, and undergo alcoholysis to form the
trialkyl phosphite derivative. Phosphorous trifluoride is only slowly hydrolyzed by water, but
reacts readily with alakaline solutions. In contrast, phosphorus triiodide is an unstable red solid
that reacts violently with water. Phosphorous trichloride in particular is an excellent synthon for
most trialkyl phosphines.

As with other P(III) compounds such as trialkyl phosphines, phosphorous trihalides can be
oxidized to the analogous phosphene oxide, e.g..

Phosphorous trihalides form Lewis acid-base complexes with main group metals, but the bonding
to dn (n ≠ 0) transition metals occurs in the same manner to that of trialkyl phosphine, i.e., with
dπ-pπ back donation. In fact one of the first examples of complexation of phosphorous to a low
oxidation metal was the formation of PF 3 complexes with Fe-porphyrin.

Phosphorous pentahalides

The reaction of white phosphorous with excess halogen yields the pentahalides. However, the
pentafluoride is best prepared by halide exchange,.

The pentaiodide is unknown, however, selected physical properties are given for the others in.

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 CHEMISTRY OF MAIN GROUP ELEMENTS

Selected physical properties of phosphorous pentahalides.

Compound Mp (°C) Bp (°C)

PF5 -93.78 -84.5

PCl5 166.8 160 (subl.)

PBr5 100 106.0

The structures of the phosphorous pentahalides are all trigonal bipyramidal in the gas phase .
Phosphorous pentafluoride maintains the trigonal bipyramidal structure in solid state, but the
chloride and bromide are ionic solids, [PCl4]+[PCl6]- and [PBr4]Br, respectively. The tetrahedral
[PCl4]+ ion is also formed with the reaction of PCl5 with other chloride ion acceptors, and.

The structures of (a) PF5 and (b) PCl5. The crystal structure

of phosphorous pentabromide.

All of the pentahalides undergo thermal decomposition,.

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Careful hydrolysis of the pentahalides yields the oxide of the appropriate trihalide,, while
excess hydrolysis yields phosphoric acid,.

OXYHALIDES AND THIOHALIDES

The oxyhalides may be prepared from the corresponding trihalides by reaction with organic
peroxides or ozone: they are sometimes referred to as phosphoryl halides.

The thiohalides, also known as thiophosphoryl halides may be prepared from the trihalides by
reaction with elemental sulfur in an inert solvent. The corresponding selenohalides are also
known.

The oxyhalides and thiohalides are significantly more electrophilic than the corresponding
phosphorus(III) species, and present a significant toxic hazard.

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