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CHEM 1101 | CHEMISTRY AND PERIODICITY OF GP 15 ELEMENTS

VSEPR

 The shapes of molecules containing a central p-block element tend to be controlled

by the no of electrons in the valence shell

 Each valence shell electron pair on the central atom E in a molecule EXn containing
E–X single bond is stereochemically significant and repulsions between them
determine the molecular shape

 Electron-electron repulsions decrease in the order

Lone pair-lone pair > Lone pair-bond pair > Bond pair-bond pair

 When the central atom E is involved in multiple bond formation to atoms X, electron-
electron repulsions decrease in the order

Triple bond-single bond > Double bond-single bond > Single bond-single bond

 Repulsions between bonding pairs in EXn depend on the differences between the
electronegativities of E and X; electron-electron repulsions are less the more E–X
bonding density is drawn away from the central atom E

 In other words, electrons are drawn away from the central atom and are hence
further apart and less repulsion occurs. The more electronegative the atom, the less
the electron repulsion and the bond angle decreases

 Note: The model does not account for steric factors, in which case steric repulsion is
outweighed by electronic effects

For 8 electron pairs, a

square anti-prism
shape is obtained

For trigonal bipyrimidal,

the bonds on the axial
group would be longer
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Distortions of tetrahedral molecule

 If the presence of the lone pair has no geometric consequence, it is termed

stereochemically inactive

 Stereochemical inert pair effect refers to the tendency for the pair of valence s
electrons to adopt a non-bonding role in a molecule or ion

 When this effect operates, VSEPR will fail

 Stereochemically inactive lone pairs are usually observed for the heaviest members
of a periodic group

 Example: [SbCl6]- and [SbCl6]3-

[SbCl6]- is predicted to be octahedral (6 electron pairs)

[SbCl6]3- is predicted to be pentagonal bipyrimidal (7 electron pairs) but it turns out to
be octahedral

Group Trends

 The valence shells of N, P, As and Sb are all similar and there are some similar
stoichiometries e.g. EH3 but there is little resemblance between the characteristics of
the compounds of P, As, Sb and Bi when compared to N

 Sum of first 3 IE decreases and the lower OS (+3) is increasingly stable wrt higher
(+5)

Example: R3P  R3P=O (cf amine and the oxidation process from +3 to +5 OS
becomes less likely down the Group)

Group 14: organic compounds formally +4, Sn exists as +2 (more stable) and +4
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state

 Elements become increasingly electropositive down the Group (increasing metallic

character). While compounds of P are covalent (as in N), As, Sb and Bi exhibit
cationic behaviour

 Atomic radii increases smoothly with increase in principal quantum no

 While the oxides of P are acidic, the oxides become increasingly basic down the
Group

 Down the Group, E—H and E—C bond strength decreases (expected) but E—F and
E—Cl bond strength exhibits anomalies, where bond to Cl is weaker than that to F

 Reason
-  bonding only in EH3 and E(CH3)3: decrease in overlap integral down the Group
leads to weaker bond, valence orbitals are more diffuse, smaller overlap integral,
weaker bond
-  and  bonding (down EF3 and ECl3) series: weaker  bond partially compensated
by  overlap
- Comparing EF3 and ECl3, bond weakens as heavier halides are descended

 Consider P: [Ne]3s23p33d0 which contains an empty d orbital. If there is correct

symmetry, overlap of P’s d orbitals with filled orbital of X leads to delocalisation and
hence partial  bonding. However, N’s d orbitals are too far away from valence
electrons to be involved in any overlap

Nitrogen Phosphorus
Very strong p-p bonds Weak p-p bonds
N2 is thermodynamically stable P2 is thermodynamically unstable and
only observed at > 900oC
Example: P(OR)3 exists but N(OR)3 cannot be prepared. Instead, O=N(OR) is
obtained as there is p-p bonding between N and O
p-d bonding is rare Weak to moderate but important d-p
N does not have proper symmetry (d and d-d bonding
orbitals are too far away from
valence shell to be used)
Oxides with amines (R3N+—O-) and phosphines (R3P=O). Bond between
phosphorus d and oxygen p orbital

Bonding to TMs:
R3P stablises electron rich metals (i.e. M(0) with low/zero OS) through a 
electron system.
R3N stablises metals in high OS (i.e. M(II)
Reason: P can use d orbitals to accept electron density from electron-rich
metals
No valence expansion Valence expansion
Obeys octet rule and maximum Coordination no of 5 and 6 are
coordination no = 4 common
N: max CN = 4 (e.g. NH4+)
P: CN in PF5 (trigonal bipyramidal) = 5 (sp3d hybridised)
CN in PF6- (octahedral) = 6 (sp3d2 hybridised – using valence bond model)
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Phosphorus (Phospho: light, Phorein: bringing)

 Discovered in 1669 by Henning Brandt from reductive distillation of putrified horse

urine

 Patented in 1851 by Thomas Albright using bone + carbon

 Used in 19th Century match industry – Lucifers (strike anywhere matches containing
white P) vs safety matches (red P). Phossy jaw was an occupational disease of those
who worked with white P

 Today, P is produced commercially by

2Ca3(PO4)2 + 6SiO2 + 10C  P4 + 6CaSiO2 + 10CO

Allotropes

 Yellow / White phosphorus is a waxy solid and exists as discrete P4 molecules; a

tetrahedral molecular solid / van der Waals’ solid. It is soluble, especially in CS2,
volatile and pyrophoric (spontaneously combust)

 Red phosphorus is air stable, insoluble and not volatile as it exists as a polymer. It is
prepared by heating P4 in a vacuum

 For other allotropes, heating to higher temperatures leads to increase in cross

linkages in the polymer

 The most stable allotrope is black phosphorus and is obtained by heating to 1600oC
and 100 atm

P4 (g) ⇌ 2P2 (g) (at 900oC)

P2 vs N2

2E2 ⇌ E4

 Thermodynamically, if N forms N4 (3 single bonds), H = 480 kJ mol-1 compared to

956 kJ mol-1 if it forms N2 (1 triple bond). Hence, N2 is preferred

 However, if P forms P4 (3 single bonds), H = 600 kJ mol-1 compared to 485 kJ mol-1 if

it forms P2. Hence, P4 is favoured

Electronic reason

  bonding overlap integrals are similar for N and P and varies proportionally less
down the Group

  overlap is much more effective in first row elements than those below (much
reduced  overlap in P than N, resulting in weaker bond as p orbitals become longer
not fatter down the Group)
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 Catenation (tendency to form single bonds) increases down the Group (similarly for
O2 and S8)
Isolating elemental As, Sb and Bi

 As: by thermolysis of FeAsS ore to give FeS and As

 Sb: Sb2S3 + Fe  FeS + Sb

 There are fewer allotropes for As, Sb and Bi

 Yellow As and Sb are comparable to P4 while other allotropes of As, Sb and Bi are
similar to ‘black phosphorus’ which contain multiple cross linkages

Comparing NH3 and PH3

NH3 PH3
Highly soluble in water Not very soluble in water
Kb = 10-5 Kb = 10-28 (very poor base, unlikely to
gain H+)
Ka = 10-29 (poor acid)

PH3 + H+ ⇌ PH4+
Gives alkaline solution Gives neutral solution

 Note: the above differences are due to differences in electronegativities NH3 contains
polar bonds while PH3 contains non-polar bonds

Synthesis of PH3

Lab

 PCl3 + LiAlH4  nucleophilic substitution

 Ca3P2 + H2O  hydrolysis

 P4 + I2 + H2O  PH4I oxidation

PH4+ + KOH  PH3 acid base

 Industrially, P4 + 3KOH + H2O  PH3 + KH2PO4 (alkaline hydrolysis)

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Nomenclature

Trialkyl (or triaryl)phosphine Trialkyl (or triaryl)phosphine Trialkyl (or triaryl)phosphine

oxide sulphide

Na+R2P-

Phosphorus trihalide
Phosphorus oxyhalide (aka
Phosphoryl halide) Sodium dialkyl (or aryl)
phosphide

Trialkyl(aryl)phosphite Phosphoric acid (aka

Trialkyl (or aryl)phosphate
orthophosphoric acid)

Hypophosphorous acid
Phosphinic acid (unknown) Phosphorous acid (aka
Phosphonic acid)
 

Alkylphosphinite Dialkylphosphonate
Tetra-alkyl phosphonium salt

Trihalides EX3 (X=F, Cl, Br)

 Synthesised directly from reaction of the elements with the halogens

E (s) + 3/2 X2  EX3

 Exception: PF3 in which P is oxidised directly to +5 OS (in PF5) since F2 is highly

oxidising
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 Volatile and rapidly hydrolysed by water

PCl3 + H2O  H3PO3 + H2PO4 (phosphoric acids)

 Structure of PX3, AsF3, AsCl3, SbCl3, SbBr3 are all trigonal pyramidal as predicted by
VSEPR

 However, BiF3 is an ionic lattice with CN=9 and SbF3 is a lattice with 3 Sb—F (highly
distorted octahedral)

 PCl3 is an important precursor to organic compounds and can convert alcohols to

alkyl halides and carboxylic acids to acyl chlorides

 PI3 is a powerful deoxygenating agent and can convert sulfoxides to sulphides

 SbF3 (Schwartz’s reagent) is a powerful fluorinating agent (R3PS  R3PF2)

 AsCl3 is used as a non-aqueous solvent

 Comparing NCl3 with NI3,

NH4Cl + Cl2  NCl3 is an explosive and the vapour is used to bleach / sterilise flour

I2 + NH3  I3N—NH3 and is shock sensitive since 2NI3  N2 (g) + 3I2, where the
reaction is thermodynamically driven by NN bond formation (entropy)

Pentahalides EX5 (EN since N cannot undergo valance expansion)

EX3 + X2  EX5

 PF5 is a gas, PCl5 and PBr5 are solids and PI5 is unknown

 All are off-white or yellow moisture-sensitive materials

 Predicted structure: trigonal bipyramidal

NMR

 Chemical shift (where the peak occurs) – information on the no of different chemical
environments for protons e.g. CH3CH2Cl has 2 different peaks

 Coupling pattern – information on no of equivalent protons on nearest neighbours

e.g. CH3CH2Cl: the –CH3 group causes the –CH2 group to split thrice (quartet) and the
–CH2 causes the –CH3 group to split twice (triplet)

 Note: Since –CH2 is closer to the electronegative Cl, it lies more to the left of the
spectrum

 Since 31P and 19F have both I= ½ (same as 1H), same rules apply
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 For PF5, experiment shows that all F atoms are equivalent, unlike what is predicted
from theory (trigonal bipyramidal, with axial and equatorial F atoms)

 Reason: Fluxionality / dynamic behaviour – the axial and equatorial places exchange
rapidly making the 2 sets of F atoms look the same. The mechanism of rotation is
Berry pseudo–rotation

 The process is very rapid as the activation energy between the interconversion
(trigonal bipyramidal to square pyramidal) is small

D3h C4v D3h

(square based pyramid intermediate)

 Common for AB5 systems e.g. Fe(CO)5

 However, though electron diffraction in gas phase gives the D3h structure, PCl5
solutions conduct electricity, indicating the presence of ions

 Since Cl does not have I = ½, there is no coupling (no other I=1/2 species to couple
with) and there are 2 chemical environments (i.e. 2 phosphorus containing species)

 Hence, the structure is phase dependent

 X-ray crystallography reveals that the compound is a salt containing [PCl4]+

(tetrahedral, Td) and [PCl6]– (octahedral, Od)

 For PBr5, it is a canary yellow solid and is an electrolyte in solution (i.e. ions present)
and 31P NMR shows only 1 environment (no coupling)

 X-ray shows that it is a salt made up of [PBr4]+ and Br– (unlike PCl , this is not a second P-containing
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species)

 Note: PBr5 is thermally unstable (PBr5 ∆

→
PBr3 + Br2) and PI5 is not well known

 For AsF5, it is generally similar to PF5

 SbF5 associates through F bridges (6 coordinated species) either as linear polymers

in liquid state or cyclic tetramers in solid state

 BiF5 consists of infinite linear chains with trans linkages

 Other EX5 exhibit complex structural behaviour based on [EX4]+ ions

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Reactions of PCl3

Grignard Reagent

 Prepared by Mg(s) + RCl I 2 , ether RMgCl

→

 Useful as a source of nucleophile R– (e.g. RCl, RCO2H, R(C=O)R), changes

polarisation on C from + to –

 3RMgCl + PCl3  R3P + 3MgCl2

 Results in formation of tertiary phosphines

 Reaction requires dry solvent (ether) to prevent protonation of R– to get alkane and
reaction proceeds in a stepwise manner, allowing mixed phosphines to be prepared

 Example: PCl3 MeMgCl

→
MePCl2 EtMgCl
→
MeEtPCl PhMgCl
→
MeEtPhP (trigonal
pyramidal)
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 Grignard reagents are structurally complex in solution (not R-Mg-X) but an

equilibrium mixture containing R2Mg, RMgX, MgX2 etc.

Tertiary Phosphines

 Compounds of type R3P (a homologous series)

 Where PMe3, PEt3, PBu3 are stinking liquids and are easily oxidised in air

 And PPh3, PCy3, PBut3 are solids and are relatively slowly oxidised due to bulky
groups and can be easily handled

 Compounds are basic due to lone pair on P

 Excellent ligands for TM, especially metals in low OS

 E.g. PhCl3 + excess PPh3  Rh(PPh3)3Cl

 Note: coordinating ability depends on both basicity and steric factors

 The greater the no of alkyl groups (electron-donating inductive effect), the more basic
the phosphine

 The presence of halogens or oxygen (electron-withdrawing) reduces the basicity of

phosphines

 Reason: The extent of basicity is related to the availability of the lone pair
(i.e. PMe3 > PPh3 > PCl3 > PF3)

 Tolman cone angle refers to the angle of the metal swept out by the van der Waals’
radius of the groups attached to the P atom

 Found by starting at the position of the metal and defining a cone which just touches
the position of substituent groups

 M—P distance is set at 2.28 Angstrom

 Note: With bulky ligands, steric factors may dominate over electronic ones in
determining the coordination to the metal

 Hence, PBu3 > PPh3 > PMe3 > PH3 and PR3 > P(OR)3
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 Reason: Flexibility is introduced by O atom on P(OR)3 (rotation about O atom) as

compared to PR3 and hence, corresponding phosphite is always smaller than the
phosphine

Phosphines as Ligands

 E.g. NiCl2 + 2PMe3  NiCl2(PMe3)2 (square planar)

NiCl2 + 2PPh3  NiCl2(PPh3)2 (tetrahedral)

 Larger substituent results in larger angle (109.5 compared to 90o)

 Amines are more basic and ‘harder’, which are better ligands to metals with high OS

 Phosphines are ‘soft’ and are better ligands to metals with low OS

 ‘Hard’ – electron density is non-polarisable whereas ‘soft’ – electron density is

polarisable / easily distorted

 M(0): easy to distort electron density

M(II): becomes increasingly non-polarisable

 Across the Period, metal/acid becomes harder. Down the Group, ligand (base)
becomes softer

 O2- is small and highly charged and it is difficult to distort electron cloud. S2- is easier
to polarise

 N-based ligands are hard while P-based ligands will be softer and thus the latter
stabilises metals in low OS

Chiral Phosphines

 Pyramidal inversion is fast for ammonia and amines but slower in phosphines

 Reason: The energy difference between the valence s and p orbital on N and P
respectively. The activation energy to convert from trigonal pyramidal (sp3) to trigonal
planar (sp2) is small for N but large for P. Hence, the rate is slower for P than N

 Thus, it is possible to prepare chiral phosphines but not amines

Synthesis of Phosphites

PCl3 + 3ROH ⃗
base P(OR)3 + 3[BH]+Cl-

 Structure of P(OR)3 – tetrahedral

 All are stinking viscous liquids

 Less basic than corresponding phosphine due to electronegative O atom

 Smaller than corresponding phosphine due to flexibility of P—O—C linkage

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 Note: Under acidic conditions, PCl3 + 3ROH  3RCl + H3PO4

Oxidation Reactions of PCl3

 Oxidation of PCl3 with O2 produces Cl3P=O (phosphoryl chloride) and oxidation with
S8 produces Cl3P=S (thiophosphoryl chloride) [tetrahedral]

 Cl3P=X can then undergo analogous substitutions to PCl3 while retaining the P=X
bond (effectively inert)

 E.g. Cl3P=O + 3MgCl  R3P=O (phosphine oxide) + 3MgCl2

Cl3P=O + 3ROH ⃗
base (RO)3P=O (phosphite)

Organophosphorus Chemistry

Phosphines + Alkyl Halides (oxidative addition)  Phosphonium salt

 R3PIII + R’X  [R3R’PV]+ + X-

 Phosphonium salt formed (analogous to ammonium salt)

 E.g. [Ph4P]+Br- :tetraphenulphosphonium bromide

 Phosphonium salts are used as large cations to trap out large anions

 WITTIG REAGENTS (requires -H to be present)

 [Ph3P–CH3]+ + BuLi  [Ph3P+–C–H2]

 Ylid is formed, with opposite charges on adjacent atoms (subset of zwitterions)

 Phosphonium ylid is a zwitterion with opposite charges on neighbouring atoms

 Ylids exhibit canonical forms between the charged species (C is sp3 hybridised) and
R3P=CH2 (C is sp2 hybridised)

 Orbital overlap diagram involves  and  bonding, where C donates electron density
Cp  Pd

 Reason: C has an unhybridised p orbital and donates its electron density to the
empty d orbital on P

Phosphonium Ylids

 Converts carbonyl compounds to alkenes (>C=O to >C=CR2)

 Example: Me2C=O + Ph3P=CH2 Me2C=CH2 + Ph3P=O

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 The reaction is an example of metathesis (exchange of bonds between the 2 reacting

chemical species)

 The driving force is the formation of the strong P=O bond

 Note: Chemists apply different models for one compound depending on the context. The structure of the ylid is best
understood using the P=C bond model but the reactivity is best understood using the charge separated model

 Non-ylid P=C bond formed from elimination of HCl from a P–C bond

R2CH–PCl2 ⃗
− HCl R2C=PCl

 Note: R groups have to be bulky groups to prevent polymerisation

 Penta-alkyls (phosphoranes) are formed when reacting phosphonium salts with an

organilithium compound

 Only works if there is no -H atom

 The reaction is adduct formation (adding something without removing anything, no

substitution, no change in OS)

[Ph4P]+I– + PhLi  Ph5P + LiI

 Predicted structure pf Ph5P: trigonal bipyramidal. However, SbPh5 is a square-based

pyramid

 However, P–C bonds can be cleaved when the carbon is aromatic to form a diaryl
phosphide which is a useful reagent / nucleophile for making phosphines

Ph3P + 2Li ⃗
THF Ph2P–Li+ + Ph–Li+

 Ph2P– is bent / angular

 Ph2PLi – lithium diphenyl phosphide is a strong nucleophile

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Synthesis of Multidentate Phosphines

NH4Cl
R3P + 2Li R2PLi + LiPh LiCl + NH3 + C6H6
CH3
Br
Br

Br Br Ph2P PPh2
Br
bis(diphenylphosphino)ethane /
'diphos' / 'dppe'
R2 P PR2 CH3

bidentate ligand tridentate ligand

R2 P PR2
R2 P
 DPPE is the most common bidentate P ligand and is analogous to ethylenediamine

Making P–P bonds

 Similar to Wurtz coupling of alkyl halides (C–C bond forming reactions)

 Reagents: Na/NH3(l)

2R2PCl Na/ NH 3 R2P–PR2 + 2NaCl

→

 With small RPCl2, cyclic compounds are formed (e.g. enveloped structure with 4 P
atoms in plane but 5th P atom sticking out)
R
R R P
P P

P P
R R

 However, if R is large, an unstable P=P bond is formed and the large R group shields
P=P from any attack

 This is an example of a kinetic trap / steric shielding where large R groups cannot fit
round a ring so the normal thermodynamic product is not obtained

 Examples include benzene rings with t-butyl groups on both ortho positions and P=P
bond attached to C1

Organo compounds of heavier elements

 Exhibit many similar stoichiometries and properties but for arsonium salts, ylids,
penta-aryl atimony,

E–C bond strength and ligating ability for TM decreases down the Group

PR3 > AsR3 > SbR3 > BiR3

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Preparation of Organoarsenic compounds

 AsCl3 is not used as the starting material due to its toxicity making it too dangerous to
handle. Hence, oxide is used as the starting material
RMgX

Anomalous Properties of organostibines

 Propensity to higher coordination no (due to valence expansion)

 SbPh5 is predicted to be trigonal bipyramidal but is a square-based pyramid

 Ph2SbF is expected to be trigonal pyramidal but it is an apex-shaped pseudo trigonal

bipyramid as each Sb atom is coordinated to 4 groups

 Me2SbCl3 is predicted to be trigonal bipyramidal but is octahedral about each Sb and

1 edge of the octahedron is shared by both antimoniy

Phosphorus-nitrogen Compounds
Ph'
 May contain P–N and/or P=N Ph

P N
Ph
 Phosphazines refer to unsaturated PN compounds
Ph
 E.g. Ph3PCl2 + Ph’NH2  Ph3P=NPh’ + 2HCl

 Typical r(P=N) = 1.60 Angstrom and typical P=N–C bond angle = 120o (sp2
hybridised about N)

 Same bonding as seen in ylids (NpPd)

Pentavalent PN Compounds

PCl5 + NH4Cl  P(NCl2)n + 4HCl (where n = 3-11)

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For n=3,

 Planar (similar to benzene)

 Aromatic

 Contains P(V) and N(III)

 P–Cl bond is very polar and hence is water-sensitive

 Preparation requires dry hydrocarbon solvent

 Small rings are stabilised by pd bonding

 Cl can be substituted by nucleophilic substitution e.g. ROH, Grignard

For n=4, puckered conformation if halide is Cl. If halide is F, structure is planar

Inorganic Polymers

(NPCl2)3 150−300
→
deg (NPCl2)n