Chemistry of Phosphorus

For more details refer the following book

• Phosphorus mostly forms tri and penta-valent compounds and the latter in its
tetracoordinate form is the most commonly observed oxidation state and geometry.
• P=O is one of the strongest double bonds of heavier p block elements (P=O: 544
kJ/mol; P=S 335 kJ/mol) and for many reactions involving phosphorus (III) and
phosphorus (V) reagents, the driving force is the formation of the P=O bond (e.g.
Wittig reaction)
• Trivalent phosphorus-carbon compounds are excellent ligands with varying steric
and electronic properties and are used as spectator ligands in metal complexes for
homogenous catalysis
• Phosphates are essential for life processes and many molecules of the living
system such as DNA, ATP and phosphacreatine contain phosphate groups. ATP is
the universal currency for energy. The average adult’s need for phosphorus is
about 700 mg per day.
• Phosphorus forms many allotropes of which white phosphorus is the most reactive
and ignites in air ~30 C forming phosphorus pentoxide. This property is used in
making phosphorus bombs and smoke screen bombs.
• Since it is one among the three essential plant nutrients (N, P and K), the major
use of phosphates are as fertilizers.
• Diammonium phosphate along with ammonium sulfate and a red dye is used as an
environmentally friendly fire retardant in large quantities to control forest fires by
spraying from aeroplanes.
• Phosphorus shows formal oxidation states 3(Ca3P2, PH3), 2(P2H4), 0(P4),
+1(H3PO2), +2(H4P2O4), +3(PCl3), +4(H4P2O6) and +5(PCl5) in its compounds.
 Phosphazenes which are phosphorus-nitrogen double bonded compound
with pentavalent tetracoordinate phosphorus find use as inorganic
polymers and superbases.
 Organophosphates inhibit the functioning of the enzyme acetyl
cholinesterase which is the reason for their use in the synthesis of
pesticides and nerve gases. Unlike chlorine based pesticides, phosphorus
based pesticides degrade rapidly by hydrolysis on exposure to sunlight, air,
and soil.
 Herbicides constitute the biggest part of the world pesticide use (40%) and
glyphosate [N-(phosphonomethyl)glycine] is the most widely used
herbicide in the world and works by inhibiting a plant enzyme involved in
the synthesis of aromatic amino acids.
 Similar to petroleum, the available phosphates in the earth is depleting and
this is a looming crisis as before the end of this century, readily available
global supplies of phosphorus will start running out.
 Nearly 40% of global reserves of phosphorus as phosphates for future are
present in a single country, Morocco which has been named the future
“Saudi Arabia of phosphorus”.
 Sterically hindered phosphines along with sterically hindered Lewis bases
form frustrated Lewis pairs (FLP’s).
 1669

The Alchemist Discovering Phosphorus : a painting

by Joseph Wright ~1750
Hennig Brandt discovers phosphorus from reductive distillation of urine concentrate
by evaporating urine to dryness and distilling the residue with sand.
Na(NH4)HPO4 in the urine, on heating gets converted to sodium metaphosphate,
(NaPO3)6

Around 10 lakh tonnes of elemental phosphorus is

produced per year, mostly from fluorapatite Ca5(PO4)3F

Although about twelve allotropic forms of phosphorus have been reported, the most well
established among these are the white, red, violet (Hittorf’s) and black allotropes.
Among these, the most sensitive to oxygen is white phosphorus which has a tetrahedral
P4 arrangement of three-membered rings and the lower stability of this allotrope
originates possibly from the strain associated with the bond angles of 60. White
phosphorus has to be stored under water to prevent auto-ignition and oxidation to P2O5.
 Allotropes of Phosphorus

White Red

Black
Violet ( Hittorf’s)
PH3 ignites in air only at 150C. However, minor amounts of diphosphine P2H4, if present
along with PH3 will make it catch fire spontaneously on coming in contact with air. PH3
has the smell of rotten fish and this is one of the reasons aluminium and zinc phosphides
are used as rat bait as they slowly release PH3 upon hydrolysis attracting the pest. Its
toxicity is similar to that of cyanide as it inhibits the functioning of cytochrome c oxidase
which is part of the electron transport chain in oxidative phosphorylation and ATP
synthesis.

Zn3P2 + 6 H2O → 3 Zn(OH)2 + 2 PH3

Holmes signal is an age old technique used by sailors for making emergency lighting on
the sea surface during night. A can containing both calcium carbide and calcium
phosphide is pierced and thrown into the sea.
 PR3 CO, (cm–1) (cm–1) PR3 CO, (cm–1) (cm–1)
 CO wrt  CO wrt
P(t-Bu)3 P(t-Bu)3
P(t-Bu)3 2056.1 0.0 PPh2(C6F5) 2074.8 18.7
PCy3 2056.4 0.3 P(OEt)3 2076.3 20.2
P(i-Pr)3 2059.2 3.1 P(p-C6H4-CF3)3 2076.6 20.5

PEt3 2061.7 5.6 P(OMe)3 2079.5 23.4

P(NMe2)3 2061.9 5.8 PH3 2083.2 27.1
PMe3 2064.1 8.0 P(OPh)3 2085.3 29.2
PBz3 2066.4 10.3 P(C6F5)3 2090.9 34.8
P(o-Tol)3 2066.6 10.5 PCl3 2097.0 40.9
PPh3 2068.9 12.8 PF3 2110.8 54.7
PPh2H 2073.3 17.2 P(CF3)3 2115.0 58.9
PR3
Lowest CO stretching frequency Highest CO stretching frequency
Most donating phosphine Ni Least donating phosphine
best donor CO best  acceptor
OC
CO
Tolman’s Cone angle

The steric bulkiness of phosphines was first compared by Tolman in 1977 using what
is now well known as the cone angle determination. Tolman defined cone angle as
the solid angle formed with the metal at the vertex and the ligand substituents at
the perimeter of a cone. The distance of 2.28 Å was taken as the average distance
between the metal and phosphorus atom of the phosphines.

Nolan’s percent buried volume %Vbur

In 2010 Nolan made a comprehensive comparison using around 700 X-ray

crystallographic data of phosphines and NHC complexes especially using AuCl as the
metal unit and compared the steric properties. He defined %Vbur simply as the
percent of the total volume of a sphere occupied by a ligand when bound to a
metal. The volume of this sphere represents the potential coordination sphere space
around the metal occupied by a ligand/ligand fragment. The sphere has a defined
radius (which was fixed at 3.50 Å) and the metal to phosphine distance was fixed at
2.00Å and 2.28 Å, the latter for a one to one comparison with cone angles. %Vbur is
calculated using crystallographic data and using a dedicated software.
S. No. Phosphine Cone Angle () %Vbur for R3PAuCl
At 2.00 Å (at 2.28 Å)
1 Me3P 118 27.3 (23.3)
2 Et3P 132 31.7 (27.1)
3 Ph3P 145 34.8 (29.9)
4 iPr3P 160 39.1 (24.0)
5 Cy3P 170 38.8 (33.4)
6 t-Bu3P 182 43.9 (38.1)
7 (C6F5)3P 184 42.6 (37.3)
8 (o-Tol)3P 194 44.8 (39.4)
9 Mes3P 212 50.5 (45.0)
10 (PhO)3P 128 36.5 (31.9)
 Active site of Cytochrome c oxidase

The last enzyme in the respiratory

electron transport chain and is
located in the mitochondrial
membrane. It receives an electron
from each of four cytochrome c
molecules, and transfers them to one
oxygen molecule, converting molecular
oxygen to two molecules of water.

The Fe is pentacoordinated and binds O2

(along with the Cu) before reducing it.
This is also the site which CN- binds
during cyanide poisoning [stabilizing the
Fe3+ state and preventing its redox (Fe2+/
Fe3+) activity] (Cyanide is a very strong
ligand) also PH3 from rat poison

Summary reaction:
4 Fe 2+cytochrome + 8 H+in + O2 → 4 Fe 3+cytochrome + 2 H2O + 4 H+out
Phosphorus oxides and sulfides
Berzelius
reagent
Dithiophosphoric
acid
Glyphosate synthesis
PCl4+ and PCl6 gives
peaks at +86 and -295
ppm respectively with
85% H3PO4 as reference

Oxidative
chlorination
& Substitutive
chlorination
Phosphorus oxyacids
 Orthophosphoric acid: synthesis and uses

As arrest remover
dentistry phosphoric acid is used as an etching solution.
It is also used as a solution for anodizing,
as a buffer agent, as an electrolyte in fuel cells,
as a catalyst in many organic reactions,
a pH adjuster in skin-care products
s a sanitizing agent in dairy and brewery industry

Sodium tripolyphosphate (STPP) is the most common phosphate additive in detergent powder
Adenosine triphosphate

The energy used by human cells requires the hydrolysis of 100 to

150 moles of ATP on a daily basis. There is only about 5g of ATP in
the entire human body. Up to 40 kg equivalent of ATP is used in 24
hours. In human beings ATP molecules are recycled upto 750 times per
day.
While working with Fiske, his mentor at Harvard Medical School, he made many fundamental
and path breaking discoveries other than that of ATP. These include synthesis of phosphacreatine
which replenishes ATP while resting, methotrexate the first anticancer drug, folic acid (vitamin
B9), many antibiotics such as aureomycin, the first tetracycline and Hetrazan, the most widely
used drug against filariasis which leads to the deformity causing elephantiasis. The Fiske-
SubbaRow method of colorimetric estimating phosphorus is still one of the best methods and is in
the top 100 cited scientific articles ever with more than 20,000 citations.
 Chemical Name Industrial Name synthesis Major Uses
(Short form)

Mono Mono Fertilizer

ammonium ammonium 11–48–00
phosphate phosphate
MAP
Diammonium Diammonium Fertilizer
phosphate phosphate 18–46–00
DAP
Mono Triple Fertilizer
calcium superphosphate 00–44–00
phosphate
MCP(TSP)
Mono Single Fertilizer
calcium superphosphate 00–17–00
phosphate +
gypsum
SSP
superphosphate Ca(OH)2 + 2 H3PO4 → Ca(H2PO4)2 + 2 H2O Leavening
agent
Calcium Dicalcium CaCl2 + H3PO4 + 2 NaOH → CaHPO4 + 2 NaCl Dietary,
monohydrog phosphate + 2 H2O tableting
en phosphate H3PO4 + Ca(OH)2 → CaHPO4 agent,
poultry feed
 Phosphorus nitrogen compounds

Phosphazenes

Phosphazenes are compound having pentavlent tetracoordinated phosphorus bound

to nitrogen through a double bond. In general, they can be prepared by two different
synthetic methods namely the Staudinger method and the Kirsanov method. In the
Staudinger method a trivalent phosphorus compound is converted to the
phosphazene unit often using an azide. In the Kirsanov method one uses a
pentavalent phosphors halide and react the same with ammonia or primary amines to
realize the phosphazene unit.
 Phosphazene superbases

Non ionic and non-nucleophilic bases also have an important role in base catalyzed organic
reactions. These should be bulky so that the proton can attach to the basic center but no
alkylation or complex formation should happen. NaHMDS & KHMDS are examples of
alkali-metal based non nucleophilic strong bases. There are also many examples of bulky
amines which are non nucleophilic bases such as DBU, Hünigs base (N,N diisopropyl ethyl
amine). However, the lesser basicity and the instability of some of these bases toward O2,
hydrolysis, and electrophilic attack (e.g. carbonyls) limit their use

Reinhard Schwesinger in 1987 came out with a set of peralkylated polyamino acyclic
phosphazenes, which are extremely strong, uncharged non-nucelophilic bases with a high
level of steric hindrance. These compounds, now also known as Schwesinger bases or
phosphazene superbases can be fine tuned to obtain a range of basicities and has been
applied to many organic reactions with excellent success.
The above reaction does not proceed with n-BuLi, NaOBut or P1-tBu bases
 Verkade’s superbases (Proazaphosphatranes)
Verkade`s superbases which are ball shaped proazaphosphatrane molecules, are very strong
bases due to the extraordinary stability of their protonated forms where the phosphorus center is
stabilized by the distal nitrogen as well. Verkade`s bases are about 8 orders of magnitude
stronger as a Lewis base than any amine known, including the well known diazabicyclo 5,4,0
undecane (DBU) and diazabicyclo 4,3,1 non-5-ene (DBN).
Cyclophosphazenes
Isomerism in cyclophosphazenes
Nerve gases and their activity
Frustrated Lewis Pairs