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Aim of the paper: The paper is mainly about P-block metals.

The P-block in the periodic table is spread over 6 groups, from group 13 till group 18, but the paper will focus primarily on 3 groups, which are groups: 14, 15 and 16. These three groups contain the most important elements that concern a chemist when it comes to study the P-block of the periodic table. The study of a block in the periodic table is considered more of a descriptive study of the whole block and its elements, so basically the paper will present an overview on all elements in theses three groups, the general trends, the oxidation numbers and the different compounds they form. P-block elements (general trends):

Figure 1 (The P-block elements)

(As aforementioned, the paper will be mainly focusing on the elements of groups: 14, 15 and 16.) The P-block occupies the upper far right region of the periodic table. The valence shell of the P-block elements has the notation: ns2np1-6, where n represents the shell. The s sub-shell is always fully filled with 2 electrons and the p sub-shell is filled according to each element in a specific group, and the p sub-shell can accommodate 3 orbitals so it can be filled up to 6 electrons.

In general, the P-block groups always begin by non-metals; metalloids then end with metals, which are the heaviest elements of the group. (See the figure above) Going down a group: there is an increase in the metallic properties (increase in basic character), increase in ionic radius, consequently a decrease in ionization energy. An important fact also in P-block is that π bonding becomes less important in going down a group, and that will be more clearly explained through out the paper. In addition, conductivity increases and that’s because of the small separation of valence and conductance bands in heavy elements with big ionic radii. Across a period: the metallic character decreases, decrease in ionic radius, which infer that there is an increase in the covalent character (acidic character), and a decrease in the ionization energy because of the small ionic radii. The valence shell is given by: ns2np1-6, which infer that the maximum oxidation state for group 14 elements is +4, for group 15 elements +5 and for group 16 elements is +6. The oxidation numbers of the P-block are very numerous and range from negative to positive values and have a maximum of +4, +5 and +6 for groups 14, 15 and 16 respectively. However, there are always exceptions. For example, the lead of group 14 is expected to have a maximum oxidation number of +4, but it is experimentally found that the most dominant and stable oxidation number for lead is +2. Also for group 16, the oxygen is expected to have +6 as the maximum oxidation number, but in fact it never reaches that high oxidation number, the most common oxidation number known for oxygen is generally -2. On the other hand, the sulfur in the same group possesses oxidation numbers that range from -2 to +6. Those exceptions are due to a specific stability reason called: “the inert-pair effect”. Inert pair effect is basically the tendency of the outermost s electrons to remain unionized or unshared in compounds of post-transition metals. It’s related to the increasing stability of oxidation states that are less than the group valency for the heavier elements of groups 13, 14, 15 and 16. In other words, in most cases, heavy P-block elements prefer to possess lower oxidation numbers because they are more stable that way. Solids in group 14 usually exist as crystals, in group 15 they usually exist as allotropes – different structures of the same element, e.g. ozone and oxygen (O3 and O2) –. In group 16, oxygen has a maximum CN of 4,

although its congeners, such as sulfur and other elements have CN of 5 and 6. Group 14 includes carbon, which is one of the most important elements on mother earth and that is the base of all organic compounds. Most of group 14 elements form strong complexes with halogens and oxygen. Group 15 elements form strong complexes with nitrogen and oxygen. Group 16 includes oxygen, which is the 2nd most electronegative element after fluorine existing in group 17 and that is important in almost all chemical processes.

I) GROUP 14: Some of the elements – the carbon family - are found in nature. Carbon is mined as diamond, graphite and coke. A new allotrope of C was also discovered and it’s called “buckminsterfullerene” C60. Carbon exists in atmosphere as carbon dioxide and dissolved in natural waters and insoluble in carbonates of calcium and magnesium. Silicon exists as sand, quartz and clay, and it represents 26 % by mass of the earth’s crust. Germanium does not usually occur naturally only found in zinc ores. Tin is artificially produced. Lead is obtained from sulfide ores. These elements have wide industrial uses. C as coke or coal is used in fuel, as diamond in jewellery, as graphite in pencils and lubricants. Si is used in semi-conductors. Ge is used in transistors and Pb is used in plumbing due to its softness and malleability. Carbon forms: Although diamond and graphite are 2 allotrope crystals of carbon, it was found that diamond is effectively an electrical insulator and graphite is actually a good conductor. The origin of these different physical properties actually arises from the different structures and bonding in the 2 polymorphs. Graphite is the good conductor; the graphite crystal is composed of sheets separated by gaps called “the van der waals gap”. The electrical conductivity is mainly related to the delocalized π bonds existing in the graphite structure. In these gaps, atoms and ions of reducing and oxidizing agents can penetrate, so graphite acts as electron acceptor and

in some cases electron donor. The compound formed is called “intercalation compound”. Carbon clusters (metal and non metal clusters) are known to have the shape of the soccer ball. They are mainly formed when an electric arc is stuck between carbon electrodes. Many fullerenes (carbon clusters) are formed among which the most dominant is C60 the buckminsterfullerene and small quantities of others such as: C70, C76, C84. The X-ray crystallography of C60 showed that the molecule consists of 5 and 6 membered carbon rings. This was extremely useful in the identification of carbon nanotubes that were found to have their structure endings having fullerene-like caps containing these 5 and 6 membered rings.

Figure 2 (C60 fullerene)

The synthesis of fullerene-metal complexes is basically related to their redox and coordination chemistry. C60 can react with electron rich metal complexes as well as strong electrophiles and oxidants to yield oxo bridge complexes. All these are interactions to form complexes outside the fullerene cage. “Enohedral fullerenes” are formed as well. These endohedral fullerenes can accommodate atoms inside the C60 cage, which means that metal atoms are trapped inside the cage.

Figure 3 (Pt metal trapped inside C60 fullerene)

Partially crystalline carbon is the form of carbon that has a low degree of crystallinity. In other words, the carbon crystal is amorphous. This form of carbon has considerable commercial importance that include: carbon black used as filler for rubber goods, activated carbon used as adsorbent and carbon fibers. Group 14 compounds:  With “Hydrogen” to form “Hydrides” All group 14 elements form tetravalent hydride “EH4”. Carbon with hydrogen forms the basis of organic compounds, the hydrocarbons. Alkanes: CnH2n+2, alkenes: CnH2n and alkynes: CnH2n-2. The stability of long chains C-C bonds or multiple bonds C=C and triple bonds, and C-H is attributed to the strong bond enthalpies. Silicon with hydrogen forms silanes. Silanes are analogous to alkanes, but the longest chain contains only four silicon atoms Si4H10. Silanes are much more reactive than alkanes and their stability decreases with increasing chain length. This reactivity is due to the large radius of Si, which means that there are available empty d-orbitals that can accommodate electrons and facilitates the formation of complexes. Also Si-H is much more polar than C-H. silanes can not be hydrolyzed in water, they are hydrolyzed in acidic solutions very readily. Silane itself is considered a reducing agent. Hydrosilylation is analogous to hydroboration of alkenes. Ge, Sn and Pb with hydrogen form unstable hydrides. This is because the stability of hydrides decreases on going down a group in the P-block.

 With “Halogens” to form “Halides” All group 14 elements form tetrahalides. Sn forms stable dihalides as well due to the inert pair effect of oxidation state that was aforementioned. Halogens replace the hydrogens in methane to form tetrahalomethane. The rate of this nucleophilic displacement is as follows: F<Cl<Br<I. the carbonyl halides are usually planar molecules and they are useful chemical intermediates. For example, CCl4 is a very famous solvent in many chemical reactions. Tetrahalides are mostly known for silicon and germanium. Si and Ge halides are mild Lewis acids and can interact with one or two ligands to yield 5 and 6 coordinate complexes. Substitution reactions are more readily to occur with Ge and Si halides rather than carbon halides because Si and Ge can expand their coordination sphere (due to their large radii) to accommodate the incoming nucleophile. Tin can form both tetra and dihalides. And that’s because Sn possesses both +2 and +4 oxidation states. On the other hand, Pb cannot form tetrahalides because it does not possess the +4 oxidation state. The inert pair effect forces Pb to form dihalides only. PbCl2 is extremely stable compared the very unstable PbCl4.  With “Oxygen and Sulfur” to form “Oxides and Sulfides” Among the most famous oxides, they are basically the most well-known oxides of carbon: carbon monoxide (CO) and carbon dioxide (CO2). They are both gases, CO is known for its toxic behavior when it binds to Fe in haemoglobin and prevents O2 from attaching to our blood so the person suffocates. On the other hand, CO2 is known for its greenhouse effect. Both CO and CO2 are very common ligands in d-metal chemistry. They form metal complexes, but CO2 is much less important in that field. CO and CO2 act as the Lewis acid, and by donation of CO and CO2 sigma bonds are formed and back donation of the electron-rich metal into antibonding π orbital of CO and CO2. As for sulfides of carbon, CS and CS2 are the most common and they are analogous to carbon oxides. Silicon oxides are confined to tetrahedral 4 coordinate Si, the tetrahedral SiO4. Structure of the molecule shows that there are 2

shared O atoms in each Si in a chain or a ring. Silicon oxides can exist also in silicate crystals, they are known as “Amorphous solids”, which are glasses. In the structure of the silicate crystal, Si-O-Si link is found all over the structure. The difference in the backbone structure of Si-O-Si link is what determines its identity, whether it’s a mineral or polymer for example. Now, let’s see the oxides of the metals of group 14. Germanium oxides: GeO is a reducing agent but it is unstable and it disproportionate into Ge and GeO2, the 4 coordinate GeO4 exists, as well as the 6 coordinate germanium crystalline that has a rultile-like syructure. As previously mentioned, down a group in P-block, the oxidation number of metals tends to be +2 because of the inert pair effect. Tin oxides: Tin oxide SnO exists as 2 polymorphs, the blue-black polymorph known for the presence of a stereochemically lone pair on the metal atom and the oxygen atoms around the metal in a square-like structure, and the red SnO that has a similar structure and it can be easily converted to the blue-black form. SnO can be further oxidized to SnO2 in presence of air or it disproportionates to Sn and SnO2 in absence of air. Lead oxides: The structure of PbO is very similar to that of blue-black SnO, in the stereochemically active lone pair existing on the metal atom. Another, very well known oxide of lead is the so called: “red lead” that has the formula: Pb3O4, it contains Pb in both +2 and +4 oxidation states in an irregular 6 coordinate environment (octahedral).  With “Nitrogen” The cyanide ion (CN-) is mainly the easiest compound formed as a result of the combination of C with N. It is isoelectronic with CO mentioned above. The only difference between both ligands is that CO is a 2electron donor neutral ligand, whereas CN- is a 2-electron donor –vely charged ligand. They are both very renounced for their role as ligands in coordination chemistry to form metal complexes, however, CN- only forms complexes with metals having positive oxidation states. It acts as a strong Bronsted base (good electron donor) and a poor Lewis acid (poor π acceptor). Furthermore, as it’s analogous to CO, it has a toxic effect as well. It attacks a certain enzyme in our body and causes the

reduction of oxygen to water, which results in rapid and catastrophic collapse of energy production. With Si, silicon nitride (Si3N4) is formed; it’s a very hard and inert compound that enters in ceramic materials industry. Also there is (H3Si)3N, the trisilylamine, which is analogous to the trimethyl amine (H3C)3N, but Si is more electronegative than C, so there is more electrostatic repulsion in (H3Si)3N, giving it the planar structure. Another difference between them is the presence of d orbitals in Si atom, which contributes in the delocalization of lone pair electrons around the N atom and makes it available for π bonding.  Carbides and Silicides: Carbides are basically binary compounds resulting from the combination of C with metals and metalloids. There are 3 types of carbides: saline, metallic and metalloid carbides. Saline carbides are divided into 3 subcategories (all resulting from combination of C with group 1 and 2 metals): the graphite intercalation compounds such as KC8 formed by a redox process, the dicarbides characterized by the presence of C22- ion in the structure. C22- is found to be isoelectronic with CN-, thus it has same properties in metal complexes formation when it acts as a ligand. The methides are characterized by the presence of C4- ion such as Al4C3, and it’s considered as a borderline compound between saline and metalloid carbide. Metallic carbides are mainly metallic compounds formed from the combination of C with d-block metals. MC binary compounds have fcc or hcp structures with the C atoms occupying the octahedral holes of the metal atoms. A C atom in octahedral holes infers that C is hyper coordinate, as six metal atoms surround it. Silicides are Si-metal binary compounds analogous to carbides (C-metal binary compounds). Si combines also with metals in group 1 and 2, and mostly with the f-block metals to form compounds with formula MSi2 the silicides usually have the tetrahedral cluster structure.  Aluminosilicates, are compounds basically formed from the substitution of Si by Al3+ ions in their silicates. Most of the structures are found to have Al3+ ions sandwiched between silicate layers. These aluminosilicates occur naturally as clays, minerals and rocks.  Organometallic Compounds:

Metals of P-block group 14, form many organometallic compounds that are of greast industrial importance. Usually they are tetravalent and have low polarity, and their stability decreases from Si to Pb. Going down the group, we’ve seen that the stability decreases and oxidation number is reduced to +2 due to the inert pair effect. Thus, Sn and Pb organometallics differ from Si and Ge organometallics in that fashion. In addition to the presence of halide bridging in Sn and Pb organometallic compounds. II) GROUP 15: Elements of group 15 – the nitrogen family - are: nitrogen (N), phosphorus (P), arsenic (As), antimony (Sb) and bismuth (Bi). As the general trend of the P-block, the group begins with non-metals (N and P), metalloids (As and Sb) then metals (Bi) at the end of the group. The group is characterized by the existence of oxidation states variety (-3 to +5), with the most common of them: +3 and +5. They all have the eletron configuration ns2np3, which gives them a kind of stability, because the p orbitals are half filled. Nitrogen is the most important element of the group. It is one of the main components that air is consisting of. It exists as N 2 (dinitrogen) in the atmosphere representiong 78 % by mass of it. N can be obtained by distillation of liquid air. Phosphorus is recovered from fluorapatite and hydroxyapatite minerals by carbon arc reduction and it is synthesized artificially in labs. Arsenic, antimony and bismuth are found in sulfide and oxide ores, they are naturally found as: As4S4, As2S3, As2O3, Sb2S3, Bi2S3 and Bi2O3. Elements of group 15 are of great importance in our life. They are used a lot both industrially and biologically. N is used as an inert gas in the industrial production of ammonia (NH3) by the famous “Haber process”. Also in the production of nitric acid by “Ostwald process”. The synthesis of ammonia provides a route to a wide range of nitrogen compounds that are used as: fertilizers, plastics, explosives, etc… also, N is biologically important as it is a major component of amino acids and proteins. In addition to the useful application of liquid nitrogen in the depression of freezing point, liquid N is a very practical and rapid way to decrease the FP. P is used in alloys, cleaning agents, plant nutrient, and biologically it exists in bones and teeth as calcium phosphates, also in cell membranes, proteins of DNA and RNA. Most importantly, substituted phosphines

(PX3) are important widely used ligands in the formation of metal complexes. As – although it’s very poisonous - is used in integrated circuits and laser. Sb is used in semiconductors and IR detectors. Going down the group the +3 oxidation state becomes more favorable relative to the +5 oxidation state, that’s why Bi the last element in the group is a useful oxidizing agent, in addition to its medical uses. Despite the great importance of N, N2 itself is strikingly unreactive. This unreactivity is due to: the great strength of N-N bond (actually triple bond), thus it requires a huge amount of activation energy to break it, the relatively huge gap between HOMO and LUMO MOs in N2 that makes the molecule resistant to electron transfer in redox reactions, and the low polarizability of N2, which discourages the electrophilic and nucleophilic displacement reactions. That’s why N2 must be activated first to react. The Haber process of industrial production of ammonia is one successful way of activating N2 as NH3 is the route to numerous compounds containing N, and that’s how N is active. Furthermore, N 2 was found to be isolelectronic to CO, and it is used as a ligand in the formation of metal complexes, by back donation of electro from the metal to the antibonding π orbitals of N2. From the electron configuration: ns2np3, +5 is expected to be the higher oxidation number. Because of the inert pair effect, this oxidation state is reduced as we go down the group, thus +3 is a more stable oxidation state for Bi. N has a variety of oxidation, it usually maintains –ve oxidation states as it is a very electronegative element, except when it reacts with elements having higher electronegativities such as: O, Cl and F; in that case N acquires +ve oxidation states. Comparing N2 and NH3 as ligands in the metal complex formation, NH3 can never endure back donation because of the absence of accessible d orbitals, thus it only bond to metals through σ bonding. Group 15 compounds  Binary compounds: Group 15 elements form binary compounds on direct interaction with many elements. With N, elements directly interact with N or NH3, these interactions can result in: saline nitrides in which the compound formed contains the N3- ion, which means that N has the -3 oxidation state, hilghy polarizable and these compounds have covalent character and occur usually with Li and group 2 elements; covalent nitrides in which E-

N bond is covalent and depends on the element to which N is attached; interstitial nitrides interaction of N with d-block elements, the N atom occupies the octahedral holes in the cubic or hexagonal close-packed lattice of metal atoms, these compounds are used mainly in crucibles. With P, like N, phosphides interact directly with all metals, the phosphide can be monophosphide  M:P = 1, metal-rich phosphide  M:P > 1, and phosphorus-rich phosphids  M:P < 1. The other elements in group 15 (As, Sb and Bi) also form binary compounds upon direct interaction with metals.  Azides: Are compounds containing the azide ion “N3-“. It’s a negatively charged ion with a -1/3 oxidation number. The azide ion is isoelectronic with CO2 and N2O (dinitrogen oxide), and it possesses a linear structure like CO2and N2O. N3- is a strong Bronsted base and it is a good ligand towards d-block ions. Thus it can form strong metal-azide complexes. One important application is: when alkali metal azides are heated or detonated by impact, they explode causin a huge liberation of N 2 gas that is used in the inflation of car air bags during accidents.  Hydrides: All group 15 hydrides are pyramidal and are characterized by the decrease of the bond angle going down the group, i.e.; the bond angle decreases in the hydride molecule from N to Bi. This decrease is due to steric effects, and as the radius increases going down the group, the repulsion between bonding pairs decreases and the bond angle is closer to 90°. Nitrogen hydrides: the most famous forms of N-H are ammonia (NH3), hydrazine (N2H4) and hydroxylamine (NH2OH). As aforementioned, NH3 is synthesized by the Haber process, which is the direct combination of N2 and H2 carried out in presence of Fe catalyst. This process was a huge success when invented, because NH3 is the primary source of almost all N containing compounds. Liquid ammonia is also considered as a perfect non-aqueous solvent for group 1 metals. Ammonia is a water-soluble weak base, it forms the ammonium ion NH4+, which forms very many important ammonium salts such as ammonium nitrates and ammonium hydrogenphosphates used as fertilizers. On the other hand, hydrazine is formed by the “Raschig process”, which is the reaction of ammonia with sodium hypochlorite in presence of d-metal ion catalyst,

the reactions proceeds through several steps. N2H4 is even a weaker base than NH3. The primary use of hydrazine and its methyl derivatives is in rocket fuel, also hydrazine is used as a foam blowing agent, N 2H4 and N2H5+ are used as reducing agents in chemical reactions of the recovery of precious metals. Hydroxylamine is useful in the synthesis of the caprolactam intermediate during the manufacture of nylon. Unlike NH3, hydrides of the rest group 15 elements are of minor importance. PH3, AsH3 and SbH3 are highly poisonous hydrides; their alkyl and aryl analogues are of greater importance. The substituted phosphines and arsines (PR3 and AsR3) are widely used in as ligands in metal coordination chemistry. The organophpsphines and organoarsines are ligands that interact mainly with central metal atoms having low oxidation states.  Halided and Oxohalides: Trihalides (having trigonal pyramidal structures) are known for all elements of the group, however, some of the heavy elements of the group can form pentahalides (having trigonal bipyramidal structures) as well. Nitrogen halides: NF3  pyramidal molecule, very unreactive (weak base) because of the electronegative F atoms that make the lone pair electrons unavailable for sharing. NCl3  electronegativies of N and Cl are almost the same, thus the molecule in almost nonpolar. NBr3  highly explosive. NI3  known only in the form of highly explosive ammoniate (NI3.NH3) N is more electronegative than both Br and I, so N acquires the -3 oxidation state whereas, both halogens acquire the +1 oxidation state. Halides of elements from P to Bi: Pentafluorides are known for all elements from P to Bi, pentachlorides are known for As, P and Sb, and the pentabromide is only known for P. there does not exist pentabromide or chloride for Bi because of the inert pair effect, only the pentafluoride exists for Bi. Oxohalides are mostly reactive gases, and the molecules are tetrahedral. Nitrogen forms nitrosyl halides (NOX, NO2X) by direct interaction of the halogen with NO or NO2, phosphoryl halides (POCl3, POBr3 and POF3) are formed by the reaction of the tetrahalide (PX3) with O2.  Oxides and Oxoanions:

Figure 4 (Frost diagram for group 15 elements)

The Frost diagram above shows that there is thermodynamic tendency for reduction of the +5 oxidation states of the elements. It shows that +3 is the most stable oxidation state for most group 15 elements. Bi(V) has tendency to form Bi(III), because of the inert pair effect, Bi2O5 is a very strong oxidizing agent followed by NO3-, then As (V) and Sb(V) are milder oxidizing agent, whereas P(V) is very weak. In most cases the intermediate oxidation states of nitrogen (especially N(III) and N(IV)) are unstable and they are susceptible to disproportionation, i.e. the ion disproportionates into two ions, one having a lower oxidation state and the other having a higher oxidation state than the original ion. N(II) such as NO, the nitric oxide is a strong π acceptor, thus it forms strong metal complexes through metal backdonation in the antibonding π orbitals of NO. N2O, N having +1 oxidation state is isolelectronic to N3-, thus they behave similarly regarding the formation of metal complexes. As for the oxygen compounds of P, As, Sb and Bi; the oxidation states range from +5 to +1, with +5 being the most common oxidation state for almost all group 15 elements except for +3 oxidation state that is increasingly more important for Bi, and that’s due to the inert pair effect.

Phosphazenes are another group of compounds that are analogous to the oxygen compounds of phosphorus, in which the oxo group is replaced by NH2 group or NR2 group. PN compounds can be open chains or cyclic or polymeric. PN compounds are also isoelectronic to SiO compounds.  Organometallic Compounds: Oxidation states +3 and +5 are the most encountered in the organometallic compounds of As, Sb and Bi. The M-C bond strength decreases for a given R group in the order As>Sb>Bi; consequently the stability of the compounds decreases in the same order. All the compounds act as Lewis bases and form complexes with d-metal ions, the basicity decreases in the order As>Sb>Bi. The strength of the M-M bond decreases in the order As>Sb>Bi as well. M-C bonds can be single; arsenic, antimony and bismuth also form multiple bonds M=C. III) GROUP 16 As mentioned in the introductory part, O is the most important element of group 16 (the oxygen family). It is chemically – significantly – different from the other members in the group. It’s the 2nd most electronegative element in the periodic table after F, thus it’s way more electronegative than all its congeners. The small radius of oxygen and the absence of accessible d orbitals make CN = 4 the maximum coordination number of O, whereas S for example can reach CN = 5 & 6. O represents 21 % by mass of the atmosphere. It’s readily available as 2 allotropes: O 2 found in air and O3, which is basically the ozone. O2 can be obtained by air liquification and distillation. Sulfur is also available in several allotropic forms: S2, S3, S7, and cyclic S8. S can be extracted by the “Frasch process”, in which underground deposits are forced to the surface using superheated water and steam and compressed air. Another way of S extraction is the “Claus process”, it’s basically extraction of S from natural gas and crude oil. S is mostly used in the manufacture of sulfuric acid that is itself used in the synthesis of very many fertilizers and as electrolyte in acid batteries. Se and Te occur in metal sulfide ores and the electrolytic refining of copper. Se has 3 allotropic forms of which the most important is the amorphous black selenium that has a very complex structure comprising rings containing up to 1000 Se atoms. Se is very important for humans, but it can be very toxic if it’s inhaled in large amounts. Te and Po are both very toxic as well and exist as crystals. All elements of group 16 except for O, have lower tendencies to form

multiple bonds unlike the oxygen, because of the poor overlap of π orbitals. It was found that Se is very difficult to be oxidized to Se(IV) due to the lanthanide-like contraction in radius following the 3d elements. Group 16 Compounds All elements are reactive to form compounds by direct reaction with most other elements except with some d metals and the noble gases.  Hydrides: Oxygen hydrides are mostly water (H2O) and hydrogen peroxide (H2O2) also called oxygenated water, and they are both liquids. The hydrides of the other elements are all toxic. Water is the most important hydride of all, and the only non-toxic hydride compound among all the hydrides formed by the group 16 elements. Water has significantly high boiling point (100°C) because of the strong hydrogen bonding between the electronegative O and H, H--O---H. Water is the most common solvent known for almost all chemical compounds. All polar compounds are soluble in water, and some covalent non polar compounds are miscible or partially miscible as well, because of the hydrogen bonding interactions. Moreover, all chemical compounds undergo hydrolysis either spontaneously or enhanced by catalytic procedures. Compared to water, oxygen peroxide has an additional O atom, thus its hydrogen bonds show more strength and toughness, that’s why it has a higher boiling point (150°C). H2O2 is relatively unstable so it undergoes disproportionation. However, it’s a very good oxidizing agent, and it has very many important applications such as: water treatment, antiseptic, paper industry, etc… Hydrides of S, Se, Te and Po are all gases and mostly toxic.  Halides: -2 is the common oxidation number for oxygen with all halogens except with F, which is the only halogen that is more electronegative than oxygen, only with F, O reaches the highest possible oxidation state +2. F brings out the highest oxidation states of all O congeners but the binary halides formed are unstable. Other halogens are less electronegative than F, thus they do not bring out the highest oxidation states with group 16 elements.

 Oxides: We’ll only focus on the oxides of the group 16, i.e. the reaction of oxygen with its congeners. The oxygen is known to be very reactive, that’s why it reacts with almost all elements in the periodic table not only the group 16 elements. SO2 and SO3 are the most common oxide forms of S, they are both gases and exist in the angular and trigonal planar structures respectively. Both are Lewis acids, S having the π orbitals available to accept electrons. SO3 is even a stronger acid with O bridging between the S atoms in the polymeric structure. SO2 (sulfur dioxide) is a poisonous gas but it is relatively important in the synthesis of sulfuric acid, it first passes through an intermediate step, which is its oxidation to SO3. SO2 is also used as disinfectant and food preservative. SO2 forms weak complexes with p-block Lewis bases and water, but it forms stable complexes with strong Lewis bases. SO3 is formed by catalytic oxidation of SO2 and it’s the intermediate step in the synthesis of sulfuric acid. Dioxides of Se, Te and Po are prepared by direct reaction of oxygen with the elements. Oxohalides are most importantly formed with S, Se and Te. The tellurium oxofluoride is one of the most known oxohalides. It has the commercial name: “teflate” and it is a well-established ligand for high oxidation state d-metal complexes.  Oxoacides: Because S and O are the most important elements of group 16, chemists spent a good bunch of time studying the chemistry of S-O. They found that oxoacids of sulfur are of great importance due to the redox properties of the oxoanions. Sulfur, like nitrogen and phosphorus, forms many oxoacids. Sulfur has common oxidation states: -2, 0, +2, +4 and +6. However, there are also many S-S bonded species that are assigned odd and fractional average oxidation numbers. In general for pblock elements, many of the thermodynamically favorable reactions are relatively slow when the element is in its maximum oxidation state (+6), kinetically, the oxidation numbers of compounds containing a single S atom changes in a 2 step mechanism that requires an O atom transfer path for the mechanism. The pH has a remarkable effect on the redox effect of the oxoanions. For example, this applies for SO2 and SO32-, because SO2 is easily reduced in an acidic medium so it is a good

oxidizing agent, whereas SO32- in a basic solution is primarily a reducing agent. The oxoanions of Se and Te are less diverse and extensive compared to the oxoanions of S. However, the selenic acid (H2SeO3) is thermodynamically a strong oxidizing agent. Telluric acid Te(OH)6 or (HO)2TeO2 can be thermodynamically reduced, so it’s an oxidizing agent as well. Again there is a variety of sulfur oxoacids, they are important in the way that, they themselves, their salts and even their ions upon decomposition or hydrolysis are used as oxidizing or reducing agents. Examples of sulfur oxoacids: sulfuric acid (H2SO4), sulfurous acid (H2SO3), disulfurous acid (H2S2O5), thiosufuric acid (H2S2O3), peroxosulfuric acid (H2SO5), dithionous acid (H2S2O4), dithionic acid (H2S2O6), and polythionic acids that contain more than 2 S atoms (H2SnO6).  Metal Compounds of Group 16 elements and their Structures: Because oxygen will be always more electronegative than its partner metal in a metal compound; oxygen will be always acquiring a –ve oxidation state, whereas the metal will be having the +ve oxidation state. O can either be an oxide (O2-) with -2 oxidation state, a peroxide (O22-) with -1 oxidation state, or a superoxide (O2-) with -1/2 oxidation state. Alkali metals and alkaline earth metals usually form peroxides and superoxides. Normal metals very rarely form peroxides and superoxides. Noble metals usually do not form stable oxides; they can only have a small layer on the surface of the metal that has traces of oxygen when exposed to a source of oxygen. In a metal oxide, the oxide is a strong Bronsted base, whereas the metal ion is of low charge and radius. Metal oxides with metals having oxidation numbers: +1, +2 and +3, the metal oxide has usually high CN. M2+ oxides have the rock-salt structure (6:6 coordination), M3+ oxides have 6:4 coordination and M1+ oxides have a rutile (6:3 coordination) or fluorite structure (8:4 coordination). MO 4 compounds are molecular and have the tetrahedral structure such like the osmium tetroxide (OsO4). For the oxides of metals in higher oxidation states and the oxides of non-metals there is a different trend. It’s either the formation a multiple bond (terminal E=O linkage), which is common with the majority of p-block metals because of the presence of the stereochemically active lone pair on the metal ion; or a bridging oxygen atom as in E-O-E, having angular and linear structures.

Metal sulfides differ a lot from metal oxides, because they occur naturally as their sulfide ores from the first place. Metals are extracted primarily from sulfide ores. They can be either: metal sulfides containing (S2-), disulfides (S22-) or sulfido. Group 1 metals form sulfides (M2S) and have the antifluorite structure. Group 2 metals and some metals of the f-block form monosulfides (MS) with rock-salt structure. Light d-block metals form monosulfides as well; heavier d-block metals form disulfides containing discrete (S22-) and adopt the zinc-blende structure. Selenides, Tellurides and Polonides form metal compounds directly with the reaction of Se, Te and Po with metals. Light metals of group 1 form compounds with Se and Te having the antifluorite structure, heavier metals adopt the rock-salt structure. D-block metal compounds with Se, Te, and Po are formed upon direct interaction.  Ring and Cluster Compounds: Sulfur, Tellurium and Selenium have the ability to form a variety of cyclic and polymeric compounds containing: S-S, S-N, Se-Se and Te-Te bonds. In the cyclic or polymeric structures they can act as anions or cations; that’s why they are called the polyanion/polycation compounds. They can also act as ligands, and with larger bonds to the metal; they are chelating ligands that form chelate rings. An example of a S-N polycation cyclic compound is the tetrasulfur tetranitride (S4N4). The molecule is an eight-membered ring with the 4 N atoms in a plane and bridged by S atoms that project above and below the plane. The short S-S bond distance explains the weak interaction between pairs of S atoms.

Figure 5 (Tetrasulfurtetranitride)

Figure 6 (3D-Tetrasulfurtetranitride)

Conclusion: To conclude, the hope the paper was successful to present a quite descriptive overview on the most important points that should be discussed regarding the p-block elements, and especially the elements of groups: 14, 15, and 16.

References: Burrows. "P-Block Chemistry." Chemistry3. Oxford University Press, 2009. Web. Apr. 2012. < omes/>. Shriver, and Atkins. Inorganic Chemistry. 4th ed. Oxford UP, 2006. Print. (mainly chapters: 13, 14, 15)