n=5

Trigonal bipyramid

n=6
octahedron

n =7
pentagonal bipyramid

n=8
dodecahedron

n=9
Tricapped trigonal prism

n = 10
bicapped square antiprism

n =11
octadecahedron

n = 12
icosahedron

The deltahedral cages with 5-12 vertices which are the parent cages used in conjunction with Wades rules to rationalize borane cluster structures structures. . As a general (but not foolproof) scheme, when removing the vertices from these cages to generate nido nido-frameworks, remove a vertex connectivity three from the trigonal bipyramidm any vertex from the octahedron or icosahedron icosahedron, , a cap from the tricapped trigonal prism or bicapped square square-antiprism antiprism, , and a vertex of highest connectivity from the remaining deltahedra deltahedra. .

A deltahedron (plural deltahedra) deltahedra) is a polyhedron whose faces are all equilateral triangles. triangles.

363 K in diglyme

B2H6 + Na[BH4] 4Na[B3H8] + 4HCl 5[B3H8]- + 5HBr

Na[B3H8] + H2 3B4H10 + 3H2 + 4NaCl 5[B3H7Br]- + H2

373 K

2Na[B3H8]

435 K in diglyme

3B5H9 + 4H2 + 5BrNa2[B6H6] + 5H2

O O O

1-methoxy-2-(2-methoxyethoxy)ethane 2-Methoxyethyl ether Di(2-methoxyethyl) ether Diethylene glycol dimethyl ether

triglyme

More boron chemistry will be discussed while learning Inorganic Rings, Cages and Clusters.

The Group 14 Elements [ns2np2]

Features The periodic changes among the chemistry of these elements The stability and abundance of C C-C bonded compounds The importance of -bonding in carbon compounds

Lie in the centre of the main group elements elements. . They show major differences from the lightest element carbon (a typical nonnonmetal) to the heaviest element lead (a typical main group metal). The group oxidation state is +4 (important for C and Si). In hydrocarbons the oxidation is formally -4; these compounds are thermodynamically unstable, but an extremely important class of compounds which have constituted the branch of organic chemistry. chemistry. Ge shows some stable +2 compounds; GeI2, although the +4 state is predominant. Tin ( (Sn Sn) ) shows both +2 and +4; +2 is reducing agent, whereas Pb4+ is oxidizing and Pb2+ is stable. PbO2 is a powerful oxidizing agent.

These elements in principle should show stable 2+ oxidation state using two p-electrons. Promotion of an electron from ns2 to np requires energy, but the atom can now form four bonds. More energy produced by bond formation for C and Si offsets the cost of promoting an ns electron. Tetravalent state is very stable for C and si. Bond strength decreases down the group. Important feature of Group 14 elements is catenation which is less important down the group. Important sources of carbon are coal and crude oil, natural gas (mainly as CH4) Carbon shows allotropy: Graphite, diamond (crystalline forms); soot (amorphous)

What factors contribute to the stability of strong CC-C bonds?

Catenation is the formation of rings and chains by atoms of the same element. element . After carbon, sulfur forms the next largest number of catenated compounds

a) Diamond b) Graphite c) Lonsdaleite d) C60 (Buckminsterfullerene) e) C540 Fullerene f) C70 Fullerene g) Amorphous carbon h) SingleSingle-walled carbon nanotube

Lonsdaleite is a hexagonal allotrope of the carbon allotrope diamond, believed to form when meteoric graphite falls to Earth.

In graphite, the carbon atoms form planar sheets of used sixsixmembered rings (sp2). The remaining pz orbitals form extensive delocalized -system over the sheet sheet. . Attraction between adjacent sheets is weak, so the graphite layers slide over each other very easily easily. . Graphite structure is unique for carbon among Group 14 elements, because the small pz orbitals on carbon can overlap effectively to form the delocalized -system system. . In contrast, diamond has 3D-network structure built up from tetrahedral carbon atoms forming strong covalent bonds with each other other. . Diamond is the one of the hardest substances known. known . Another molecular allotropes of carbon is called fullerenes; fullerenes; first one to be discovered is C60 consists of five five and sixsixmembered rings also called as buckyballs after the architect R. Buckminster Fuller who designed geodesic domes. domes.
The melting points of diamond and graphite are greater than 3550 oC, but C60 sublimes between 450 oC and 500 oC. Explain observation.

Silicon, Germanium. Tin and Lead

Silicon is the most abundant element (after oxygen) in the Earths crust. Occurs as silica (SiO2) and silicate minerals. Germanium is least common and occurs in some zinc and silver ores and also in flue dust and the ashes of certain types of coal. Si and Ge adopt diamonddiamond-like structures.

Tin mainly occurs as cassiterite, cassiterite, SnO2 from which metallic tin is obtained by reduction The main ore of lead is galena, PbS, PbS, which is roasted in air to form lead oxide, which is then reduced to the metal using CO in a blast furnace. Lead is a typical heavy metal.

Chemistry
All Group 14 members are fairly unreactive unreactive. . Tin and lead dissolve in a number of oxidizing and nonnon-oxidizing acids. Si and Ge are only attacked by HF but all are reactive towards halogens. Graphite can form two types of products with either buckled or planar sheets, depending on whether the -system is disrupted or not. The reaction of graphite with fluorine at 400 oC gives graphite fluoride, (CFx)n which is colorless when x=1. One of the possible structures consists of fused cyclohexane rings. Except for the edges of sheets (which will be CF2 units) each carbon bears single F. Fluorinated graphite is nonnon-conducting as -electrons are consumed. When graphite is reacted with a reducing agent such as an alkali metal, inclusion compounds are formed, e.g KC8 is an inclusion compound.

8C (graphite) + K(g)

KC8(s)

Structure of graphite fluoride

660 pm

Used as solid lubricators

K vapor

Graphite, inter layer separation 3.35

KC8
inter layer separation 5.40

CaC6
The graphite interlayer distance increases upon Ca intercalation from 3.35 to 4.524 , and the carbon carboncarbon distance increases from 1.42 to 1.444 .

Hydrides and Organometallic Compounds

Methane, CH4, is the simplest hydride of carbon; carbon; the hydrides, MH4 of other Group 14 elements are less stable owing to the size mismatch between Group 14 atom and the very small H atom atom. . Silane, germane and stannane are all known, but plumbane is very Silane, unstable and no chemistry has been determined. determined. General methods of preparation

SiCl4 + LiAlH4 GeO2 + LiAlH4

SiH4 + LiAlCl4 GeH4 + LiAlO3 4PhSiH3 + 3LiAlCl4

4PhSiCl3 + 3LiAlH4

Hydrocarbons are thermodynamically unstable in air; suitable activation (such as a spark) readily ignites hydrocarbon-air mixture (octane is a fuel)

2C8H18 + 25O2

16CO2 + 18H2O + energy

Catenation is restricted to Si10H22 for silicon Ge9H20 for germanium and only Sn2H6 is known for tin. A wide range of alkyl and aryl compounds of Si, Ge Ge, , Sn and Pb have been prepared (Me3SnCl, Et4Pb, an antianti-knock additive in petrol). For carbon, compounds containing double and triple bonds are well known. (C=C, C=O, C=N, C=P. C=P); (CC, CN, CP)

Pb

Pb

First example of a Pb=Pb compound

Does tin show multiple bonding? If so, is it different from, say C=C??

Tetrahalides MX4 exists for all group members, except for PbI4 which is a too strong an oxidizing agent to co co-exit with the reducing iodide; iodide; same thing is true with PbBr4 as well well. . Si +2Cl2 Sn + 2I2 SiCl4 SnI2 SnI4 GeBr4 + 2H2O SiO2.nH2O + HCl

GeO2 + 4HBr SiCl4 + excess H2O

All halides (except CCl4) undergo hydrolysis except SiF4; kinetic instability CCl4 can not increase its coordination number.

Sn + 2HX GeX4 + Ge 2GeI2

SnX2 + H2 2GeX2,

Adduct formation by addition of X- to SnX4

SnX 4 X-

comproportionation reaction

GeI4 + 2Ge,
SnX5-

disproportionation reaction

Sn Cl Cl
X-

Gas phase
SnX 62-

Sn Cl Cl

Sn Cl Cl
Solid State

Sn Cl Cl
n
SF6 is similarly stable towards hydrolysis

Propensity of carbon to form extensive stable chains is remarkable. The congeners of carbon (especially silicon) and other related nonnon-metals exhibit it to a reduced extent. Despite there is no thermodynamic barrier , formation of longlong-chain silanes silanes, , SinH2n+2, their synthesis and characterization are formidable tasks. Although SiSi-Si bonds are weaker than C C-C bonds, the energy difference do not account for the observed stability differences. The reason is the lowlow-energy decomposition pathways are available to silanes which is not available to alkanes (cracking (breaking C C-C bond) is a tough task). In addition to their inherent kinetic instability, silanes are difficult to handle because they are very reactive. CnH2n+2 + 3n+1 O2 2 nCO2 + (n+1)H2O

nSiO2 + (n+1)H2O SinH2n+2 + 3n+1 O2 2 In fact both the reactions are thermodynamically favored to proceed to the right. The major difference, not apparent in the stoichiometric reactions, is the energy of activation which causes the paraffins to be kinetically inert in contrast to the reactive silanes. silanes .

Further complications with silanes arise from lack of convenient synthesis and difficulties in separation. However, compounds n = 1 to n = 8 have been isolated, including straightstraight-chain and branched branched-chain compounds.
For more information read: Henegge Henegge, , E. In Silicon Chemistry; Corey, J. Y.; Corey, E. R.; Gasper, P. P. Eds.: Wiley: New York, 1988.

Why sulfur catenates: catenates:

The great variety of molecular forms that can be achieved by S-S catenation . Numerous way in which the molecules so formed can be arranged within the crystal. S-S bonds are very variable and flexible; bond distances can vary from 180180-260 pm (single bond to multiple bond character). Bond angles can vary from 9090-180o and dihedral angles SS-S-S-S from 0 0-180o. Estimated SS-S bond energy is 430 kJ/mol and the unrestrained S-S single bond energy is 265 kJ/mol. Less tendency to stabilize S=S bonds similar to O=O. But they are not as stable as CC-C bonded compounds.

Halides with EE-E bonds: Catenated Halides Similar to extensive range of hydrocarbons, diverse range of halocarbons are known; best example being poly(tetrafluoroethene poly(tetrafluoroethene), ), PTFE, an extremely stable polymer finding numerous applications
F F F F F F F F

n
F F F F F F

For silicon, a large number of higher halides are known, containing chains of silicon atoms, analogous to the polysilanes. Germanium, tin and lead form few analogues of the silicon compounds because of the lower stability of the EE-E bonds going down the group, and the increased stability of the divalent halides

When carbon or silicon is heated with many metals, carbides and silicides are formed. There are many different types of carbides, which are classified by their reaction (or lack of it) with water and the products formed. Transition metals typically form interstitial carbide compounds, in which the individual carbon atoms occupy holes in closeclose-packed metallic lattices. These materials are also very hard. Some interstitial carbides hydrolyse to give hydrogen and hydrocarbons, but others such as tungsten carbide (WC) are very hard, inert materials The carbides of reactive metals tend to be ionic in nature; some carbides (e.g. Na4C, Be2C) formally contain C4- ions and give methane on hydrolysis. Other contain the acetylide ion (C22-) and give ethyne ethyne. . Structure of CaC2 is similar to NaCl structure with C22- ions arranged in a parallel fashion. CaC2 + 2H2O Li4C3 + 4H2O C2H2 + Ca(OH)2 MeCCH + 4LiOH

Oxides
The oxides of carbon, being gases, are quite different from those of the other Group 14 elements. Structural difference results from the presence of strong p p-p bonding between carbon and oxygen. Carbon oxides are discrete species. In contrast, for silicon the Si=O bond is unstable with respect to two SiSi-O single bonds, and so silicon oxides and many oxyanions have infinite, covalent network structures of SiSi-O bonds. Heating the element in oxygen produces the dioxide, EO2. CO, CO2, C3O2 HCOOH CO + H2O (dehydration of formic acid with conc. H2SO4) HCO2- (formate anion) (with concentrated hydroxide) CO is poorly soluble in water and does not react with it. CO + OH

CO is isoelectronic with N2 and has similar physical properties.

CO is very poisonous and much more reactive than nitrogen. It combines with the halogens (except iodine) directly, for example with chlorine to give the highly poisonous phosgene gas.

CO +Cl2

COCl2

CO is an excellent ligand in coordination chemistry of transition metals. Ni(CO)4, Cr(CO)6, Ru3(CO)12, Ir4(CO)12 etc. CO compares well with PR3 in its donordonor-acceptor properties. CO2 is the most stable oxide produced on an enormous scale industrially by the combustion of coal, oil and natural gas. In laboratory, CaCO3 CaO + CO2

CO2 is soluble in water, mostly as dissolved CO2 molecules but a small amount of CO2 is hydrated to give carbonic acid, H2CO3. This is a weak acid, partly dissociates to hydrogencarbonate (HCO3-) or CO32ions. 2NaO + CO2 Na2CO3; 2OH- + CO2 CO32- + H2O

CaCO3(s) + CO2(g) + H 2O (l)

Ca(HCO3)2 (aq)

This equilibrium is very important in geochemistry, for example the deposition and redissolution of limestone rock during weathering.

CH2(COOH)2

P 4O10 -2H2O

The structural chemistry of SiO2 is extremely complex; the stable form of SiO under ambient conditions is quartz, and other highhigh-temperature (tridymite and cristobalite cristobalite) ) modifications are known. The different ways of linkages shown by SiO4 tetrahedra results in various SiO2 structures. A vast number of polymeric silicates occur naturally.
More details on polymeric silicates will be given while discussing selected polymeric Main Group compounds

GeO2, SnO2 and PbO2 have considerable ionic character and adopt rutile (TiO2) structure

Ge, Sn, Pb O

six coordinated metal and three coordinated oxygen These oxides are amphoteric, and dissolve in both acids and bases. The hydrated Sn2+ and Pb2+ ions undergo substantial hydrolysis

CS2 is a molecular substance similar to CO2. The species, CS, sulfur analogue of CO is unstable as a free moleule moleule, , but can be stabilized by coordination to a metal. Several transition metalmetal-CS complexes are known. [RhCl RhCl(CS)(PPh (CS)(PPh3)2 The compounds ME and ME2 (E = S, Se, Te) are known for Ge Ge, , Sn and Pb. Pb.

Polyatomic Anions of the Group 14 Elements

When alloys of heavy Group 14 elements (Ge (Ge, , Sn, Sn, Pb) Pb) and alkali metals are dissolved in liquid ammonia or en, polyatomic anions are produced. These can be crystallized if a donor ligand ligand, , such as a crown ether is added to the solution to complex the alkali metal cation cation. . Known polyanions are Sn42-, Ge42-(tetrahedral), Sn52-, Pb52- (TBP), and Sn92- (predict the structure using Wades rules).

CS is not stable above -160 oC, many MCS compounds can be made

S M M C C S M S M M C M M

S C M C M M S M

Linear CS is a better -donor and -acceptor than CO, but depends on electron richness of the metal Very few homoleptic thiocarbonyl complexes are known. Ni(CS)4 is unstable at room temp. Many mixedmixed-ligand complexes are known with properties similar to those of pure carbonyl complexes. Cr(CO)5(CS), (6-C6H6)Cr(CO)2(CS), Cr(CO)3(CS){P( (CS){P(OPh OPh) )3}2, Fe(CO)4(CS)

{Fe(CO) 4]

2-

CSCl2

{Fe(CO) 4(CS)]
PR3

CS2

Mn L OC CO

Mn OC OC S

-L

CS

- S=PR3

Mn OC

CS CO

RhCl(PPh3) 3 + CS2

trans-RhCl(CS)(PPh3)2

+ S=PPh3

(Me3P)2(CO)2Fe( -CS2Me)
Free CS, CS , M3(3-CS), M2(-CS), M-CS, 1273 cm-1 1040 1040-1080 cm-1 1100 1100-1160 cm-1 1160 1160-1410 cm-1

Na/Hg

Fe(CS)(CO)2(Me3P) 2

Group 15 (Pnictogen (Pnictogen) ) Elements: N, P, As, Sb and Bi

Oxidation states of +3 and +5 occur for all elements +3 state is most stable for bismuth due to inert pair effect +5 is stable for phosphorus, but acts as an oxidizing agent with nitrogen, arsenic and antimony antimony. . Arsenic with completely filled 3d inner shell which is relatively poorly shielding, is rather more difficult to oxidize to the +5 state due to added inert pair effect effect. . The -3 oxidation state occurs in the hydrides such as NH3, and in anions such as P3- (Na3P). P).

N
N N N

N N

N N N
N5+

N N N

Because N2 is a very stable molecule, both thermodynamically and kinetically, other species comprised of nitrogen atoms are rare rare. . *N5+ was isolated in 1999. 1999 . The authors of the view that high energy ionic allotrope of nitrogen N5+N3may be isolated isolated. . Another nitrogen compound is N8.
*K. *K.O. Christe, Christe, W.W. Wilson, J.A.Sheehy and J. A. Boatz, Boatz, Angew. Angew. Chem. Chem. Int Int. . Ed Ed. . Engl. Engl. 1999, 1999 , 38, 38, 2004 2004. .

N N
Azidopentazole

High energy energy-density materials materials. . Scope of making many other homoatomic nitrogen species species. . Some important pseudohalides

Azide Cyanide Cyanate Thiocyanate

N3CNNCONCS-

Behavior is similar to halide ions

In covalent azides azides, , the N3 group behaves as a pseudohalogen pseudohalogen, , so that the molecules (N3)2 and N(N3)3 are also potential nitrogen allotropes, analogous to Cl2 and NCl3, respectively. respectively.

The principle source of phosphorus is phosphate rock, a complex calcium phosphate. Reduction of phosphate rock gives white phosphorus, with a tetrahedral structure which persists in solid, liquid and gaseous state. When P4 vapour is heated to 800 oC, appreciable amount of triply bonded P2 molecules are formed. Prolonged heating of white phosphorus in a sealed vessel results in the formation of red phosphorus, a relatively inert form of the element, with a poorly defined but complex structure. However, the most stable allotrope is black phosphorus, formed by heating phosphorus at high pressure, which has several structures; the rhombohedral form has a layer structure.
Arsenic, antimony and bismuth occur predominantly as sulfides. These three elements form layered structures related to black phosphorus

P
P P P P P P P P

P P P P

P P P

P P

white phosphorus
P P P P P P P P P P P

red phosphorus
P P P P P P

sublimation 2n P n

P P

The structure of rhombohedral black phosphorus

Hydrides
All five Group 15 elements form hydrides EH3, but with different trend in their physical and the chemical properties. Boiling points increase on going town the group, with the exception of the anomalously high boiling point of NH3, which is due H HN-H hydrogen bonding. The HH-E-H bond angles also decrease going down the group, owing to the decreasing EE-H bond strengths. Thermal stabilities decrease down the group. Enthalpies of formation parallel the E-H bond energies for these compounds. fHo (kJ mol-1) NH3 PH3 AsH3 SbH3 -46.2 +9.3 +172.2 +142.8 E-H bond energy (kJ mol-1) +391 +322 +247 +255

Single, double and triple bond strengths for N-N and P-P bonds are given given. . Show that these are consistent with the occurrence of nitrogen as solely a triple bonded diatmoic molecule. molecule. The NN triple bond energy is more than three times that of the single N-N bond energy, so N-N single bonded allotropes are unstable relative to N2. The NN bond energy is also greater than the sum of the N=N and N-N energies (in a N=N N=NN=NN=N - form), so this is also unfavorable relative to the NN NN. .

Rationalize the trend in the HH-E-H bond angles in the series of hydrides Molecule NH3 PH3 93.5 AsH 92 SbH3 91.5

E-E single, double and triple bond energies for nitrogen and phosphorus Bond Bond energy (kJ mol-1) NN +160 P-P +200 N=N +419 P=P +310 NN +945 PP +490

H-E-H bond angle (o) 107

All have tetrahedral arrangement (3BP +1LP); angles are expected to be <109.5o Owing to the effect of the lone pair. Distortions to the basic shape is due to the difference in electronic distribution in the E-H bonds. The N-H bond short (101.5 pm) and the nitrogen is more electronegative than hydrogen, so the bonding pair will reside close to the central N atom, occupying more space in its valence shell. These N-H bonding pairs will repel each other more, widening the bond angle.

N H H H H

Sb H H

NH3 manufacturing: N2 + 3H2 2NH3 [ high pressure and temp, catalyst)

Liquid ammonia (B.P. -33 oC) has comparisons with water as a solvent; H3O+ and OH- are respectively an acid and a base (a proton acceptor) in water, while in ammonia, NH4+ is an acid and NH2+ is a base.

Phosphine, PH3
2P4 + 12H2O 4H3PO3 5PH3 + 3H3PO4
Ultrapure PH3: (thermal disproportionation of phosphorus acid (H3PO3)

PH3 + 3H3PO4 4EH3 + 3Li[AlX4] 2PH3 + 3Ca(OH)2

4EX3 + 3Li[AlH4]

Hydrolysis of metal phosphide: Ca3P2 + 6H2O