The Group 13 elements ‘There are some clear trends in chemical properties of the Group 13 elements, such as oxidation number and amphoteric character, that we shall see repeated in the ‘other groups of the p block. In thie chaptar we look at ‘the occurrence and isolation of each element in Group 13 ‘and consider the chemical properties ofthe elements and their simple compounds, coordination compounds, and ‘orgarometallc compounds, In addition, weintroduce the ‘extensive range of boron clusters. ‘The elements of Group 13, boron, aluminium, gallium, dium, and thallium, have diverse physical and ‘chemical properties. The frst member of the group, boroa, is essentially nonmetallic whereas the prop A cl = erties of the heavier members of the group are dis- tinctly metallic. Aluminium is the most important —\~ element commercially and is produced on a massive scale for a wide range of applications. Boron forms a large number of cluster compounds involving hydrogen, metals, and carbon. Gallium and indium in alloys and compounds have important electronic and optical properties. Seen zz- PART A: THE ESSENTIALS In this section we discass the essential features of the chemistry of the Group 13 elements. 13.1 The elements ‘Key points: Boron the only nonmetal inthe group. Aluminium isthe most abundant Group 13 element. ‘The elements of Group 13 shaw wide variation in abundancein crustal racks, the oceans, and the atmosphere. Aluminium is abundant but thelow cosmic and terrestrial abundance ‘of boron, like that of lithium and beryllium, reflects how he light elements are sidestepped in nucleosynthesis (Section 1.1). The low abundance of heavier members of the group is in ‘keeping with the progressive decrease in nuclear stability of the elements that follow iron. Boron occurs naturally as borax, Na,B,O,(OH),.8H.O, and kernite,Na,B,0 (OH),2HO, from which the impure element is obtained. Aluminium occurs in numerous clays and aluminosilicate minerals but the commercially most important mineral is bawxite, a ‘complex mixture of hydrated aluminium hydroxide and aluminium oxide, from which it is extracted on an immense scale. Gallium oxide oceurs as an impurity in bauxite and is normally recovered as a byproduct of the manufacture of aluminium. Indium and thallium occus in trace amounts in many minerals. ‘Whereas the elements of the s and d blocks are all metallic, the elements of the p block ‘ange from nonmetals, through metalloids, to metals. This variety results in 2 diversity of chemical properties and some distinctive trends Section 9.4). There isan increase in metallic Port A: The essentials ma m2 23 “he laments Compounds Boron dusters Port B: The detail na Bs ns a7 ne ng 1310 mn ap naa a4 1315, a6 1a 1318 119 1320 ceuence ard recovery Uses ofthe elements and their compoueds ‘Simple byes of boron Boron vihalides Boron —nygen compounds Compounds of bors with nitrogen ‘etal brides Higher soranes and borolides Netallaboranes and carboranes “he hytides of aluinium ‘and galium ‘ihaldes of duminiam, glum, iedium, and tala Lowonidationstate tlds of. -Auminiam, gallium, ndiun, ‘nd thallium ‘Ceo compounds of aluminium, ‘plum, inium, and thalim ‘ues of galium, nium, and thalige Compounds with Group elements Zn phases ‘crganonetalc compounes DaERCISES(a) tb) Figure 13.1 A view ofthe 8, icosahedon in athombohedtal boron (a) along and () perpendicular tothe threefold axis of the ‘yal The individual icosahedra ae linked by 3c.2e bonds. 13 elements “Table 15.1 Selected properties ofthe elemerts e a Ga 7 (Covalent radis/pm 80 mss 10S Netalieradivs/pm 3 oat 16 0m len radius, "7pm 7 3 a 4 8 Neking point /*C 230066030 17M Boling point/°C 3930 ©2470 28002000460 Fistionzation energy, I/(U mol) m7 sn 56 (580 Secondionizaton energy L(t) 242718199] “hr oszation energy, Kd mc!) eso 252063 2k 2B Eectron afi E, ld md) 27 045892 Pauling electenegatty 20 16 18 rr 20 +126 eran /y 089-188) ‘character from B10 TI:B is a nonmetal, Als essentially metallic, although it is often classed asa metalloid on account ofits amphoteric character,and Ga, I and Tare metals. Associ« ated with this trend isa variation from predominantly covalent 0 ionic bonding inthe com ‘pounds ofthe elements that can ke rationalized in terms of the increase in atomic radius and related decrease in ionization energy down the group (Table 13.1). Because the ionization energies of the heavier elements are low; the metals form cations increasingly readily down the group. In contrast to the expected trend in electronegatvity Section 1.9), Ga exhibits the alternation effect (Section 9.2c), being more electronegative than Al. ‘As we discussed in Section 9.8 the first member of each group diflers from its congeners ‘on account of its small atomic radius. This difference is particalarly evident in Group 13, where the chemical properties of B are distinct from those ofthe rest of the group. How ever, B does have a pronounced diagonal relationship with Siin Group Mz 1. Boron and silicon form acidie oxides, #,O, and SiO,; aluminium forms an amphoteric 2. Boron and silicon form many polymeric oxide structures and glasses. 3. Boron and silicon form llammable, gaseous hydrides; aluminium hydride isa solid. ‘The valence electron configuration of the Group 13 elements is ns*xpt and, as this config- uration suggests, all the elements adopt the +3 oxidation state in their compounds. However, the heavier elements of the group also form compounds with the metal inthe +1 oxidation state and this state increases in stability down the group. In fact, the most come ‘mon oxidation state of Tl is TID. This trend is particularly evident within the halides and isa consequence of the inertpar effect (Section 9.5). The consequences of the inert-pair effect are evident in Group 13. Thallium() is intensely poisonous because its ionic radius is very similar to that of potassium and sodium ions: it enters cells and disrupts the mechan- ‘gms of porassium and sodiam transport (Section 27 3) Boron exists in several allotropes. Amocphous B is a brown powder but the hard and reiractory crystalline B forms shiny black crystals. The three solid phases for which crys tal structures are available contain the icosahedral (20-faced) B,, unit as a building block (Fig. 13.1). This cosabedral unitis a recurring motif in boron chemistry and we shell meet it again in the structures of metal borides and boron hydrides. The icosahedral unit is also found in some intermetallic compounds of other Group 13 elements, such as Al,Culi,, RhGa,, and K,Ga,,. Boron is inert, and under normal conditions finely divided B is ate tacked only by F, and HNO,. Even chough Al is aa electropositive metal itis very inert on account of the presence of 1 passivating surface oxide film. If ths film is removed then Al is rapidly oxidized by air. ‘Aluminium has a high reflectance, which is maintained in the powdered form, making ita useful component of silvercoloured paints. It is a good thermal and electrical conductox. Gallium is britle at low temperatures but liquefies at 30°C. Its low melting point is at~ tributed to its erystal structure, in wich each Ga atom has only one nearest neighbourand six next-nearest neighbours: thus, the Ga atoms tend to form GaGa hhas the widest liquid range (30—2420°C| of any element with the exception of Hg and Cs. Unlike Hg, Ga wets glass and skin, makingit more diffcuk to handle. Gallium readily forms alloys with other mezals and diffuses into thei lattices, making chem britele. Indium forms a distorted cep lattice and T1 is hexagonal close packed. 13.2 Compounds ‘Key point: All of the elements form hydrides, oxides, and halides in the +3 oxidation state. The +1 ‘ovidation stae becomes more stable down the group and is the most stable oxidation state for com pounds of thelium. ‘A most striking feature ofthe lighter Group 13 elements is thei ns*np! electron configura tion, which contsbutes up to a maximum of six electeons inthe valence shell when three covaleat bonds are formed by electron sharing. Asa result, maay of their compounds have an incomplete octet and act as Lewis acids, being able to complete ther octet by accepting 2 pair of electrons from a donor. Moreover, ass typical of an element atthe head of its ‘group, the chemical properties of Band its compounds ace strikingly diferent from those ofits congeners. ‘A note on good practice Be careful to distinguish electon deficiency fram the possession of an incomplete octet. The former refer to the lack of sufficient electrons to be able to acount for the ‘connections between atoms 2s normal covalent bonds; the later is the possession of lss than eight ‘electrons in a valence shel, ‘The binary hydrogen compounds of B are called boranes. The simplest member of the series, diborane, B,H, (1), electron deficient and is structure is commonly described in terms of 2e2e and 3c,2e bonds [Section 2.11): bridging 3c,2e bonds are a recurring theme in borane chemistry. All the boron hydrides burn with characteristic green flame and several of them ignite explosively on contact with ait. Alkali metal tetrakydridoboranates, NaBH, and LiBH,, are very useful in the laboratory as general reducing agents and as precuriors for most boronhydrogen compounds. Boron trihalides consist of trigonal-planar BX, molecules. Unlike the halides ofthe other clements in the group, they are monomeric in the gas, liguid, and solid states. Boron tri= fluoride and boron trichloride are gases, the tribromide is a volatile liquid, and the tiiodide isa solid (Table 13.2). This tread in volatility is consistent with the increase in strength ‘of dispersion forces with the number of electrons in the molecules. Boron trihalides have ‘an incomplete octet and are Lewis acids. The order of Lewis acidity is BF, < BCI, = BBr, 1 of electronegativty of the attached halogens (Section 4.8) partially removed by X~Bz bonding between the halogen atoms rise to the partial cccupation of the vacant p orbital on the B atom by electrons donated by the halogen atoms (Fig. 13.2). The trend in Lewi from more efficient XB 1 bonding for the lighter, smaller halogens, the F=B bond being ‘one of the strongest single bonds known. ‘The most important oxide of B, B,O,, is prepared by dehydration of boric acid. 4B(OH),\s) 28,0,(5) + 64,00) ‘The vitreous form of the oxide consists of a network of partially ordered trigonal BO, units. Crystalline B,O, consists of an ordered network of BO, units joined through O atoms. Metal oxides dissoive in molten BO, to give coloured glasses. Boron oxide and “Table 13.2 Properties ofthe boron tinaldes es Meking pom 127,107 4650 Boling pany" 1001310 Bordlengt/er = 130, 75,—T210 AG7Aumi") 12 = +21 Figure 13.2 The bonding xorbitls of boron tial ae largely localized on the electonecative halogen atons, but overlap with a p erital af boron is sgifcant in the a," orbital(mca me 2 Borazine, BN, 3 AlCl, silica aze the main constituents of borosilicate glass, which, because of the low thermal expansvity of the glass due ta the strong =O honda, is used to make heat-resistant lahoe ratory glassware. ‘There are many molecular compounds that contain BN bonds and many of them are analogous to carbon compounds. The similarities between compounds containing BN and ‘CC units can be explamed by the fact that these units are isoelectronic. The simplest com pound of B and N, boron nitride, BN, is easly synthesized by heating boron oxide with a nitrogen compound (Box 13.1): B,0,()+2NH,@) —2= 5 2BN6)+3H,0@) ‘The stricture of one form of boron nitride consists of planar sheets of atoms like those in ‘graphite (Section 14.5) and some of the physical properties of BN are similar to those of ‘graphite. For example, both graphite and BIN have a slippery feel and are used as lube ‘cants. However, BN isa white, nonconducting solid, nota black, metallicconductor Apart from layered boron nitide,the best-known unssturated compound of Band Nis borazine, B\N,H, (2), which is isoelectronic and isestructural with benzene and, ike benzene, is 2 ‘colourless liquid (b.p. 55°C). ‘The elements Al, Ga, In, and Tl are metals with many similarities in their chemical prop- erties Like B, they form electrondefcient compounds that acts Lewis acids. Aluminium forms alloys with many other metals and produces light, corrosioneresistant materials. ‘When Al is alloyed with Ga, the Ga prevents the formation ofthe tightly held passvating oxide film on the Al. Whea the alloy is dropped in water the Al reacts with the water, forming aluminium oxide and liberating hydrogen. This reaction has been suggested as a solution to the problem of storing hydeogen for use in fuel ces. However, the energy cost of recysling the aluminium oxide and gallium mixture to metallic Al and Ga makes this application unlikely. ‘Aluminium hydride, AIH, is a solid that is best regarded as saline, like the hydrides of the sblock metals. Unlike CaH, and NaH, which are more readily available commer- ion is so small, the trifluorides are mechanically hard ionic solids that have much higher melt- {ng points and sublimation enthalpies than the other halides. Their high latice enthalpies also result in them having very limited solubility in most solvents, and they do nor act as Lewis acids o simple donor molecules. The heavier tihaldes of Ai,Ga, and In are soluble ‘variety of polar solvents and are excellent Lewis acid. The ti ‘monomer occurs only at elevated temperatures in the gas phase. Otherwis exist as M,X, dimers in the vapour phase and in solution, The volatile solids are dimeric. [An exceptiog is AICI, which has a sixecoordinate layer structure in the solid phase and ‘converts to lour-coordinate molecular dimers at its melting point. The dimers contain co» ordinate M~X bonds in which & lone pair on X belonging to one AIX, unit completes the octet of M belonging to the second MX, unit (3. This arrangement cesult in a tetrahedral arsangement of X atoms around each M arom, In contrast ta the other elements in the ‘group, TIA) is the most stable oxidation state of che halides. Hexagonal Loon aide was frst developed to meet the reeds of the ‘aerospace industry It is stable in oxygen and isnot atacked by steam telow 900°C. Sa good thermal insulatr, has low thermal expansion, and is resistant to thermal shack These applications bave led to its use in industy to make hightemperature crucbles. The powder is used as a ‘ould celease and thermal insulator. Boron nitvide narotubes have been formed by deposit beron and nitegen on a tungsten surface under igh vacuum. These narotubes could be sutatle for hightemperature ‘conditions usder which carbon nanotubes would bur “The softness and shesn of powdered boron nitide has led to ts widest application, in the cosmetics and personal car industries. It is rontoxc and presents no known hazard, ar Is added v0 many progucts up to around 10 per cent. It adds a pearlescent sheen to preductssuch 1 nail polishes and lipsticks, and is added to foundations to hide ‘winks. ts ightseecive properties scatter the light, making wrinkles less noticeabie.‘The most stable form of ALO,, avalumina, is a very hard, refractory, and amphoteric ‘material. Dehydeation of aluminium hydroxide at temperatures below 500°C leads to the formation of yralumina, which is a metastable polyerystalline form with a defect spinel structure (Section 3.96) and a very high surface area. The a and y forms of Ga,O, have the ‘same structures as their Al analogues. Indium and thallium form In,O, and TI,0,, Thallium also forms the Til) oxide and peroxide, T,O and T1,O,, respectively. ‘The mostimportant oxosalts of Group 13 are the alums, MAM(SO, ),-12H,O, where Mis ‘a univalent cation such as Na*, K*, Rb*, Cs*, TI", or NH,*. Gallium and In can also form analogous ees of salts of this type but B and Ti do not: a B atom is too small and a TI atom is too large. The alums can be thought of as double salts containing the hydrated tri- valent cation [AI|OH)P*. The cemaining water molecules form hydrogen bonds beeween the cations and sulfate ions. The mineral allan, KAI(SO, ),.12H,O, from which aluminium takes its name, isthe only common, waterssoluble, aluminium-bearing mineral. It has been "used since ancient times as a mordant to fx dyes to textiles. The term ‘alum’ is used widely to describe other compounds with the general formula M'M’#(SO)),-12H,O, where Mis often a d metal, such as Fe in ‘ferric lum’, KFe(SO),.12H,0. 13.3 Boron clusters Key point: Boron forms an extensive range of polymeric, cageike compounds which include the bero- ‘hydrides, metallaboranes and the carboranes. In addition 10 the simple hydrides, B forms several series of neutral and aniosie polymecic cage-like boronhydrogen compounds. Borohydrides are formed with up to 12 B atoms and fall into three classes called closo, nido, and arachno. ‘The borohydrides with the formula [B,Ef” have a closo structure, a name derived from the Greek for ‘cage’. This series of anions i known for n= 5 wo 12, and examples include the trigonal-bipyramidal [B,H,}” ion (4), the octahedral [B,H,P~ ion (5), and the icosahe~ ral [B,,H1,P” ion (6). When boron clusters have the formula'B,H,, they adopt the nido structure, 3 name derived from the Latin for ‘nest’. An example is B,H, (7). Clusters of formula B,H.,, have an arachno structure, from the Greek for ‘spider’ (as they resemble ‘untidy spiders” webs). One example is pestaborane(11) (8,H, , 8). Boron forms many metal-containing clusters called the metallaboranes. In some cases the metal is attached to a borohydride ion chrough hydrogen bridges. A more common and generally more robust group of metallaboranes have direct MB bonds Closely related to the polyhedral boranes and borohydrides are the carboranes (more formally, the carbaboranes), a large family of clusters that contain both Band atoms. An analogue of BH (9) is the neutral carborane B,C,H, (10). oo s By 7 10 closo-,2-8,C,H,cap nme PART B: THE DETAIL In this section we present a more detailed discussion of the chemistry of the elements of Group 13, interpreting some of the “observed properties in terms of the trends from nonmetallic £0 metalliccharacter dowa the group and the impact of the income plete octet and associated Lewis acidity on theie properties. The properties of horon ace dealt with separately. 134 Occurrence and recovery Key points: Aluminium is highly abundant: thallium and indium are the least abundant ofthe Group 13 elements. Boron exists in several hard and refractory allotropes. The three solid phases for which erystal structures are available contain theicoszhedral (20-faced) B,, unit as a building block (Fig. 13.1) This icosahedral unit i a recurring motif in boron chemistry and we shall meet it again inthe structures of metal borides and boron hydrides. The icosahedral unit is also found in some in- termetallic compounds and Zint! phases (Section 3.8c) of other Group 13 elements such as Al,CaLi,, RbGa,, and K,Ga,,. Boron occurs naturally as borax, Na,B,0,(OH), 8H,O, and emite, Na,B,O,(0H),2H,0, from which the impure element is obtained. The borax is converted to boric acid, B(OH), and then to boron oxide, B,O,, The oxide is reduced with magnesium, and washed with alkali and then hydrofluoric acid. Pure B is produced by reduction of BBr, vapour with H,: 2BBr,(g)+3H,(e) > 2B(s)+6HBr(e) Aluminium is the most abundant metallic element in the crustal regions of the Earth and makes up approximately & per cent by ‘mass of crustal rocks. I occurs in numerous clays and alumino- silicate minerals bue the commercially most important mineral is bauxite, a complex mixture of hydrated aluminium hydroxide and aluminium oxide, from which it is extracted by the Hall Heroult process on an immense scale (Section 5.18). In this process the hauxite is dissolved in moiten eryolite, Na,AlF, the Imivture is electrolysed and aluminium is deposited at the Cathe ‘ode. The process is very expensive but this expense is offset by the scale of production, the availability of the raw material, and the use of hydroelectric power. The oxide, alumina, occurs nat- urally as ruby, sapphire, corundum, and emery. Gallium oxide occurs 3s an impurity in bauxite and is normal- ly recovered as a byproduct of the manufacture of aluminium. ‘The process results in the concentration of gallium in the residues from which ic is extracted by electrolysis. Indium is produced as, 4 byproduct of the extraction of lead and zinc, and is isolated by electrolysis. Thallium compounds are found in flue dust, which is dissolved in dilute sulfuric acid; hydrochlors acid is then added to precipitate thallium(!) chloride and the metal is extracted by electrolysis. 135 Uses of the elements and their compounds Key points: The most useful compound of boronis borax; the most com: ‘mercallyimportant element is aluminium. ‘The main use of B is in borosilicate glisses. Borax has many do- rmestic uses, for example as a water softener, cleaner, and mild pes tice. Borie acid, BOF), is used 28 a mild antiseptic. Amorphous ‘brown boron is wed in pyrotechnics toimpart a bright green colour, Boron is an essential micronutrient in plants. Lightweight, strong boron filaments are used in composite materials for the aerospace industry and in sports equipment. Many compounds of B are su perhard macerials, having hardness approaching that of diamond. ‘Cubic boron nitride is synthesized at high pressures, which makes it expensive. Rhenium diboride does not require high pressuresso pro duction is rdatively cheap, but Re is an expensive metal. The mater- {al known as *heterodiamond’, sometimes labelled BCN, is formed. ‘rom diamond and boron nitride by explosive shock synthesis. These ‘compounds ae used as substitutes for diamond in cutting tools and. ‘Hades. Sodium perborate, NaBO,, is used 28a chlorine-ree bleach, in laundry products, cleaning materials, and tooth whitenet. It is, less aggressive to textiles than chlorine bleaches and active at low ‘temperatures when mixed with an activator such as eetraacoryleth- ylenediamine, which is commonly abbreviated to TAED. Borares ‘sed to be popuar as fuels for rockets but were found to be t00 pyrophoric to be handled safely. Boranes are being investigated as, possible hydrogen storage materials with the hydrogen stored asthe ammonia-borane complex NH,-BH, (Section 10.4 and 13.3). ‘Aluminium is the most widely used nonferrous metal. The technological uses of aluminium metal exploit its lightness, re sistance £0 corrosion, and the fact that itis easily recycled. Ieis, used in cans, foil, utensils in construction, and in aircraf alloys (Box 13.2). Many Al compounds are used as mordants, in water and sewage treatment, in paper production, 25 food additives, and for waterproofing textiles. Aluminium chloride and chlo rohydride are used in antiperspirants and the hydroxide is used. 1 an antacid. Sodium tetrahydridoaluminate, NaAlH,, doped with TIE, is used as a hydrogen storage material Because the melting point of Ga (30°C) is justabose room tem perature, itis used in high-temperature thermometers. Gallium, and In form a lowsmelting-point alloy that is used as the safety vice in sprinkler systems. Both elements are deposited on glass, surfaces to form corrosion-esitant mirrors, and ln,O, doped with Sais used a a transparent, condacting coating for electronic displays and as a heatreflective coating for light bulbs. Gallium. nitride is used in blue laser diodes and is the basis of Bluray tech ‘ology. Iti insensitive to ionizing radiation and is used in solar calls in satellites. Gallium arsenide isa semiconductor and used in integrated circuits, lightemitting diodes and solar cells. Thallium. compounds were once used to treat ringworm and as a rat and. ant poison. However this application has been banned because of theie very high toxicity, which arises from the transport of T” {ons across cell membranes together with K* ions (Section 26.3). ‘Thallium is absorbed more effcientiy by tumour cells and has, ‘een used in nuclear medicine as an imaging agent. 13.66 Simple hydrides of boron “The simplest hydride of boron is gascous diborane, B,H, High- er boranes exit and can be liquids such at BH, and sols such 45 BH, The boranes are cleaved by Lewis bases. (@) Boranes ‘ey points: Diborane can be synthesized by metathesis beweena boron halide and a hydride source; any ofthe higher boranes can be preparedlightening the load “The ciemical and physical properties of aluminium make it the mast widely used nonferous metal islig,hashigh eectical and thermal conductviy, high refiectance, and is easily machined. These properties are erhanced by the impervious oxide layer on the surice, which eiakes i resitant 10 conesion. Howes, aluminium i aft and lacks sencth, and alloying the ‘metal with small amounts (ypicaly less than 2 percent by mass) of other clement gives a much more desirabe weight to strength aia. The properties of the alloys depend on the chemical coeposion and ‘procesing involved. In workbardering aloys suength is achieved by the ‘amount of cold work’ applied tothe alloy, for example by rolling. In heat ‘ueatabe o:precntation alos the stength ard properties are achieved boy heat treatments of varying complexity Binary, tetiary, quaternary, and ‘more complex allys are used commercial. An Al/Min ally isthe oldest ‘and most widely used. kalmest alvays contains traces of Siand Fe, which (ive added strength and hardness. Al/A alloys have good ductity and omexion resistance but are les strong, A/S alloys have goed fuity and ate used in weldag wits. AVL alloys have vey low deasties and high nest elasticity. ding Cu to this alay increases the density but also increases, the stength and caresion esinance. The greatest use of alumisium alloys worldwide isin building and ‘constuction, where they are used to male vals, roo, gutter, window frames, and doors Their strength, weight, and weather resstance make ‘them particularly appropriate for these applicatios. nthe USA and Europe, packaging has replaced contraction as the majx consumer of aluninium loys as they are impermeable to gas, flexible, and recycladle. They are ‘used 19 make dink cans easyopen Ids, aerosol cans, tl—paper—plastic, laminates, and sheets and fols. A growing application is in tanspon, where weight ang fuel consumption are serious issues. Ax AI/CU/Mg alloy i used in arraft and an Al/Ci alloy is sed in satellites and space vehicles. The use of aluminium alos in car is inceasingly prvalere and they ar used to make boty panels, engine blocks, wheels, bumpers, radiata, aed tins, Around the hone aluminium alloys are wed to make ‘ooking utensils refrigerator bodies, airconditioning wits tos, toes, and cllapible toothpaste and cosmetic tubes. by the partial pyrolysis of diborane; all the boron hydrides ae flammable, sometimes explosively, and many of them are susceptible tohydrelysis. Diborane, B,H., can be prepared in the laboratory by metathesis ‘ofa boron halide with either LiAIH, or LiBH, in ether: SLIBH, (¢t)+4BF, et) > 3LIBF,(et)+2B,H,(g) ‘That this reaction is a metathesis (an exchange of partners) can be seen by writing it in the simplified form IBH;{et) + BE,(et) > 28F{et) + BHlg) Both LiBH, and LiAIHL, like LiH, are good reagents for the transfer of H-, but they are generally preferred over Lifl and NaH because chey are soluble in ethers. The syathesis is carried ‘out with the stect exclusion of air (ypically in a vacuum line ‘because diborane ignites on contact with air) Diborane decom- poses very slowly at room temperature, forming higher boren hydrides and a nonvolatile and insoluble yellow sold that cone sist of B,gH, and the polymeric species, BH. ‘The compounds fall into two classes. One class has the fore ‘mula BH,,, and the other, which is richer in hydrogen and less, stable, has the formula B,H,. Examples include pentaborane (11), BLH,, (8), tetraborane{10), B.H,, (11), and pentaborane(9), BH,()Thenomenclatue,in which ue numberof Batomsisspe- cifed bya prefixand thenumber of Hatomsisgivenin parentheses, should be noted. Thus, the systematic name for diborane is, diborane(6); however,as there isno diborane(8),the simpler term ‘diborane’ is almost always used. TB Hy All the boranes are colourless and diamagnetic. They range from gases (BH, and B,H,), through volatile liquids (BH, and B,H,, hydrides), to the sublimable solid B,oH,,. All the boron hhydrides are flammable, and several of the lighter ones, includ- ing diborane, react spontaneously with air, often with explosive violence and a green flash (an emission from an excited state of the reaction intermediate BO). The final product of the reaction is the hydrated oxide: BH,(g)+30, (g) > 2B(OH),|s) The lighter boranes are readily hydrolysed by water: BH, (@)+6H,O() > 2B)OH), (aq)+ 6H, () [As described below, B,H, is a Lewis acid, and the mechanism of this hydrolysis reaction involves coordination of H,O acting as «a Lewis base. Molecular hydrogen then forms as a result of the combination of the partially positively charged H atom on O ‘with the partially negatively charged H atom on B. (b) Lewis acidity ‘Key points: Soft and bully Lewis haces cleave diborane symmetrically: ‘more compact and hard Lewis bases cleave the hyérogen bridge unsym- metrically, although it reacts with many hard Lewis bases, diborane is best rgarded asa softLewis cid. [As implied by the mechanism of hydrolysis, diborane and many other light boron hydrides act as Lewis acids and are cleaved by reaction with Lewis bases. Two difierent cleavage patterns have been observed, namely symmetric cleavage and unsymmetric cleavage. In symmetric cleavage, BH, is broken symmetrically into rwo BH, fragments, each of which forms a complex with a Lewis base: # | H Ka Ne Many complexes of this kind exist. They are interesting partly Iecause they ate isoelectronic with hydrocarbons. For instance,(cap am the product of this reaction is isoelectronic with 2,2-dimethyl- propane, C(CH,),. Stability trends indicate that BH, is + soft Lewis aci, a illustrated by the reaction HB-NCH,),+FB-S(CH), + H,B-S(CH,),+B-N(CH,), in which BH, transfers to the soft S donor atom and the harder Lewis acid, BF, combines with the hard N donor atom. ‘The direct reaction of diborane and ammonia results in un- ‘symmetrical cleavage, which is cleavage leading to an ionic product: om aN Me ‘Unsymmetrical cleavage of this kind is generally observed when diborane and a few other boron hydrides react with strong, ster- ically uncrowded bases at low temperatures. The steric repul- sion is such that only ewo small ligands can attack oae B atom the course of the reaction. EXAMPLE 13.1 Using NMR to identity reaction products Explain how "BNNR coud be used to determine whether cleavage of ‘dorane with an NhRinactve Lewis bac ie symmetical ar uneymmeical (secon 5). Answer We need to dently the possible products ef the wo reactions and ‘then decide how the features oftheir NMR spectra wl ciffer. Symmetrical lavage of BM, wit Lyelds BH, + BH,Land unsymmetical deavage Yyslds BNL? and BH, In the former, "8 i cupled tothe equivalent *H ruclei ad we would therfore observea quartet in the NMR spectrum. In tursymmetical cleavage the first product has" coupled 1 twoequivalent 4 nuclei, which would produce a tiplet. The second product has "8 ‘coupled tout equvalent nucle, whieh would produce 2 quintuple. ‘Selftect 12.1 "B nuclei have I~ 3. Pradict the numberof lines and thir reative intents inthe NMR specrum of BH. () Hydoboretion Key points: Hydrotoration, the reaction of diborane with alkenes in ‘ther solvent, produces organoboranes that are useful intermediates in ‘synthetic organic chemistry. ‘An important component of a synthetic chemists repertoire of reactions is hydroboration, the addition of HB across a multiple bond: HBOOR, + H,C=CH, 8 4CH,CH,BH, +R,0 From the viewpoint of an organic chemist, the C-B bond in the primary product of hydroboration is an intermediate stage in the stereospecific formation of C—H or C=OH bonds, ro which it can be converted. From the viewpoint of the inorganic chemist, the reaction isa convenient method for the preparation of a wide variety of organoboranes. The hydroboration reaction is one of ‘class of reactions in which EH adds across the multiple bond; Ihydroxilylation (ection 14.7b) ig another important example. (4) The tetrahydiidoborate ion ‘Key point: The tetahydridotorate ion is a useful intermediate for the ‘reparation of metal hydride complexes and borane adducts. Diborane reacts with alkali metal hydrides to produce salts con the tetrhydridoborate ion, BH. Because of the sen tivity of diborane and LiH to water and oxygen, the synthe ust be carried out in the absence of aie and in a nonaqueous solvent such asthe short-chain polyether CH,OCH,CH,OCH, {denoted here-polyer): BH, (polyet) + 21H (polyet) —» 2LABH,(polyed) We can view this reaction as another example of the Lewis acid- ity of BH, towards the strong Lewis basicity of H-. The BH ion is isoelectronic with CH, and NH}, and the three species show the following variation in chemical properties as the electro- ‘negativity ofthe central atom increases: cH, NH; Character: hydridic © - protic sthere'protic’ denotes Bronsted acid (proton donating) characters ‘CH, is neither acidic nor basic under the conditions prevailingin aqueous solution. ‘Alkali metal tetrahydridoborates are very useful laboratory and commercial reagents. They are often used as a mild source ‘of H™ ions, as general reducing agents, and as precursors for ‘most boron—hydrogen compounds, and they are utilized as hy= drogen storage materials (Box 13.3 and 10.4). Mose of these reactions are carried out in polar nonaqueous solvents. The preparation of diborane, mentioned previously, S1EH, +4BF, 28H, +34, (F=B,Al) is one example and NaBH, in tetrahydrofuran (THE) is used to reduce aldehydes and ketones to alcohols. Although BH; is, thermodynamically unstable with respect to hydeolysis, the’ r= action is very slow at high pH and some synthetic applications have been devised in water. For example, germane (Gell,) can be prepared by dissolving GeO, and KBH, in aqueous potas suum hydroxide and then acidifying the solution: HGeO; (ag) + BH; (ag) + 2H (oq) > Gel, (g) + B(OH), q) Aqueous BH; also can serve as a simple reducing agent, as in the reduction of aqua ions such as Ni#* or Cu** to the metal or ital boride. With halogen complexes of 4d and Sd ckments that also have stabilizing ligands, such as phosphines, tetrahy= droborate ions can be used to introduce a hydride ligand by a ‘metathesis reaction in a nonaqueous solvent: RuCl (PPh), + NaBH, + PPh, 2s, RuH,(PPh,), + other products I is probable that many of these metathesis reactions proceed through a tansiene BH, complex. Indeed, hydridoborate come plexes are known, especially with highly electropositive metals: they include AI(BH,), (12), which contains a diboraneslike dou ‘le hydride bridge, and Z<(BH1,), (13), in which triple hydride| £05389 smn Hydiogen fuel ces ae seen a an alteraivetocarbonbasd fel and a Staring to find application in mobile Tecnolages and motor vehi. fie fuel els denand an effient source of fydogen and many tmetndoogjes fr storing hydogentave been evestigated These include ee eee omgounds that generteH, on heating or on reacton with water, The ete eet ee rer omgoundshave high masprcertage iydogencostert. The values fr Lib, Nabi, Al and AlN are appronatay 1,1, TL and 10 mas er cit, respecte ‘Sedu eatnddotrate NaBH, reac wit water to generat ya gen gas nan ether eaon. [NaBH (an) + 4H,0()—> 4H fg) + NaOH) fag) 4H™=—300% mat “The reaction requires a nickel or platinue catalyst and rapidly produces ‘mais hydregen fr the engine or fuel cell The NaBH, ic ued ae 20 mace mint percent solution in water and the ful is thus a nonvolatile, ronflanmable liquid at atmospheric pessure There are no side reacions or volatile by products and the torate product can be reycled. ‘Ammonia borane, BH,NH,, with 2 fydiogen content of 21 mass, per cant, has also been invectigated for hydrogen generation. was iavestigated as a rocket fuel in the 1950s but the studies were ‘abandoned. Ammonia borane decomposes to liberate hyéioger when heated to 500°C. The wesidut is boron rite, which cannot be easily, recycled, Recent studies have investigated the hydrogenstorage potential ‘oftheammonia comple of magnesium bacokyéride Mg(BH,), 2NH, The ‘complex contains 16 mass percent hydregen, whichis released when 2 solution of the complex flows aver a ruthenium catalyst. The complex begins to decompose at 150°C, wih a maximum hydrogen release rate ‘at 205°C, making it compettive with ammonia borane BH,NH, as 2 hydogenstorage materal. bridges are present. We se from these examples that many com= pounds can be described in terms of 3<,2e bonds. EXAMPLE 13.2 Predicting the reactions of boron-hydrogen| ‘compounds by means ofa chemical equation, indicate he preducts sulting from the interaion o equal amount of HN(CH,) Cl wth iBH, in tetahydofuran Hn, Answer We sould expec UCL with fs high lattice enthalpy, 1 be a ely produc. f ths isthe case we shall be let with BH; and [HN(CH,),}". The Interaction f the hyckidc BH; ion with the prtic (HN(CH),)" son will ‘evolve hydionen to produce timethylamine and BH, In the absence of ‘other Lewis bases, the BH, molecule would coosinate to THF; however, the stronger Lewis base timetylamine is produce in the inital reactions. 4 the verl reaction wil be THN(CH,), I+ Li8H, — H, +H,BNICH,), + LiCl ‘The B atom in H,BV(CH), has four goups atacted tevahedally. Selétest 13.2 Wrte an equation forthe reaction of B,H, with propene in ‘ther solventand 21:1 stoichiometry and anothe’ equation forts reaction ‘ith ammonium clridein THF with the same stoichiometry. 12 AllBH), 13 2H), 13.7 Boron trihalides Key points: Boren trkaldes are useful Lewis acid, with BCI, stronger than BF, ard important electophils forthe formation of boron element bonds Subkaides withB—B bonds suchas 8,1, are alsoknown. All the boron srihalides except BI, may be prepared by direct reaction between the elements. However, the preferred method for BE, is the reaction of B,O, with CaF, in H_SO, This reaction, is driven in pate by prodaction of HF from the reaction of the H,SO, with CaF, and the stability of the CaSO, BO, (5)+ 3Cak (9 +6H,80,() > 2 BR (g) +3{H,O|[HSO, soln) + 3CaS0, (3) All the boron trihalides form simple Lewis complexes with suite able bases, as i the reaction BE (g) + :NH,(e)> B—NH, (5) However, boroa chlorides, bromides, and iodides are susceptible to protoljsis by mild proton sources such 2s water, alcohols, and even amines. As shown in Fig. 13.3, this reaction, together ‘with metathesis reactions, is very useful in preparative chem istry. An example is the rapid hydrolysis of BCI, to give boric BIOH),: BC, (g)+3H,0() > B(OH), (aq) +3H1Ci(aq) Figure 13.3 The eaction of boron-halogen compounds (X= halegen).cap me Iki probable thata first step in this eaction is the formation of the complex C1,B-—OH,, which then eliminates FIC] and reacts further with water EXAMPLE 13.3 Predicting the products of reactions ofthe boron tihalides Prdic he likly products the fllowing reactionsand wite the balanced ‘chemical equations (a) BF, and excess NaF in acidic aqueous Soliton, (€) BCI, and excess NaCl in aciic aqueous Solution, c) BB, and excess NM(CH), in a ytcarbon calc. Answer We need to consider whether the BX bond is susceptible to Iyayss. a) The Fiona chemical haré and fai song base, BF, is ‘hard and strong Lewis adi witha high affinity forthe Fin. Hence. the reaction shoul est in compl Fo) (a); (a) fice F and acid pevett the fomation of tydohls roduc sich 23 80H" which are formed thigh pH) Untke B~F bonds, which are very ‘tong and ony mildly susceptibe to fyb the othe: bor —halogen bends ae hySobsedvigoouslby water We can atcigate tat 8 wil undergo yds ater han coordinate toaqueeus Cr: 20, (9+ 31,0 () > B(OH), (+ 3H (9) {B00 tibrmide will urdergo prot wth formation of BN ond 204(g)+ 0 N(CH), > BOUCH)), +3 INCH) Be In this action the Hi podcad ty the rotleispotnates encase dinethyanine. Selftest 13.3 Wie and justiytalanced equations for plausible eacions between (a) Cl, and ethanol.) 2Cl, and pyridine in hydrocarbon ston (2B, and FAN), ‘The tetrafluoridotorate anion, BF;, which is mentioned in Ex- ample 13.3, is used in preparative chemistry when a relatively large noncoordinating anion is needed. The tetrahalidoborate anions BCI; and Br can be prepared in nonaqueous solvents. However, because of the ease with which B=Cl and B=Br bonds undergo solvolysis, they are stable in neither water nor alcohols. Boron halides are the staring point for the syathesis of many boron=carbon and boron=; sn compounds (Section 17.3). Examples include the formation of alkylboron and aryl- ‘boron compounds, such as trimethylboron, by the reaction of bo= +on trifluoride with a methyl Grignard reagent in ether solution: BE, +3 CH,Mgl > B(CH,), + magnesium halides ‘When an excess of the Grignard (or organolithium) reagent is present, tetralkyl or tetraayl borates are formed: 88, +Li (CH,), > LIB(CH,),}+3Li F Boron halides containing B=B bonds have been prepared. The test known of these compounds have the formula. BX, with X= CL and Br, and the tetrhedsal ster compound B Cl, The Cl, molecules are planar (14 inthe slid state but staggered (15) in the ga. Ths conformational difference suggests that rotation bout the B=B bond is quit easy, ass expected for a single bond. *Paendohlogns are specs that resemble the halogens inti chemical properties. Cyanogen, (CN, isa pseudohalegen and the cyanide ion, CN, ‘sa pseudohalide. ly em 14 BCL, Dy 15 8,0), D,, One route to B,Cl, is © pass an electric dscharge through BCI, gas in the presence of a Cl atom scavenger, sch as mer cary sapour. Spectroscopic data indicate that BCI is produced by electron impact on BCI: BC), (g) S85 BClg)+2Clig) “The Cl atoms are scavenged by mercury vapour and removed 5 Hg,Cl,(), and the BCI fragment s thought ro combine with CI, fo yield B,Cl,. Metathesis reactions can be used to make BX, derivatives from B,Cl,. The thermal stability of these de- vatives increases with increasing tendency of the X group to form a 1 bond with Bs BCI, B,0,|5)+3H,0(g) “The rapid cooling of molten B,O, or metal borates often lads to the formation of borate glasses. Although these glasses themselves have ittle technological significance, the fusioa of sodium borate ‘with silica leads to the formation of borosilicate glasses (such as Pyrex). Borosilicate glasses are resistant to thermal shock and can be heated over aflame or other source of direct heat. Sodium perborate is used as a bleach in laundry powders, automatic dishwasher powders, and whitening toothpastes. Ale though the formula is often given as NaBO,4H,O, the come pound contains the peroxide anion, O2-, and is more accurately described as Na,(B,(0,)(OH),].6H,0. The compound is pre« ferred to hydrogen peroxide in many applications because itis ‘more stable and liberates oxygen only at elevated temperatures. 13.9 Compounds of boron with nitrogen Key points: Compounds cortaining BN, which is isoelectronic with CC, include the ethane analogue ammonia borane H,NBH,, the berzene ana- logue H,N,8,H,,and BN analogues of gaphite and diamond. ‘The thermodynamiclly stable phase of boron nitride, BN, consists of planar sheets of atoms like those in graphite (Section 14.5). ‘The planar sheets of altemating B and N atoms consist of edge- shared hexagons and, as in graphite, the B=N distance within the sheet (145 pm) is much shorter than the distance between the sheets (333 pm, Fig. 13.4). The difference between the struc- tures of graphite and boron stride, however, lies in the regis- ter of the atoms of neighbouring sheets: in BN, the hexagonal rings are stacked directly over each other, with B and N atoms alternating in successive layers; in graphite, the hexagons are staggered. Molecular orbital calculations suggest that the stack- ing in BN stems from a partial positive charge on B and a partial negative charge on N. This charge distribution is cone sistent with the electronegativty difference of the two elements (XelB) = 2.04, NaN) = 3.04). ‘As with impure graphite, layered boron a slippery ‘material that is used as 2 lubricant. Unlike graphite, however, i isa colourless electrical insulator, as there is a large energy. zap between the filed and vacant m bands. The size of the band gap is consistent with its high electrical resistivity and lack of absosption in the visible spectrum. In Keeping with this large band gap, BN forms a much smaller number of intercalation compounds than graphite (Section 14.5). In contrast to graphe ite, layered boron nitride is stable in air up to 1000°C, making ita useful refractory material. Layered boron nitride changes into a denser cubic phase at high pressures and temperatures (60 kbar and 2000°C, Fig. 13.5). Figure 13.4 The sructue of lyered hexagonal boron nitide. Not thatthe sings are in egister between Lye.o 1 2 3 6 5 6 Lattice enthalpy densityiIMJ cm) Figure 13.6 The coreation of haness with atice enthalpy density (the lattce enthalpy divided by the malar volume ef the substance). The pint {or carbon represents diamond; that for boron nitride represents the diamondlike sphaleite srucure. ‘This phase is a hard crystalline analogue of diamond but, as it has a lower lattice enthalpy, it has a slightly lower mechanical hardness (Fig. 13.6). Cubic boron nitride is manufactured and used as an abrasive for certain high-temperature applications in Which diamond cannot be used be:ause it forms carbides with the ‘material being ground. “The fact that BN and CC are isolectronic suggests that there be analogies between these compounds and hydrocar boas. Many amine-boranes, the boron=nitrogen analogues of saturated hydrocarbons, can he synthesized by reaction henween a nitrogen Lewis base and a boron Lewis acid: 4B,H,+N(CH,), + H,BN(CH,), However, although amine-boranes are isoelectronic with hy- drocarbons, their properties are significantly different, in large ppart due to the difference in electronezativties of B and N. For ‘example, whereas ammoniahorane, H,NBH,, is a solid at com temperature with a vapour pressure of a few pascal, its ana- logue ethane, H,CCH, is a gas thar condenses at 89°C. This, difference can be traced to the difference in polarity of the two ‘molecules: ethane is nonpolar, whereas ammoniaborane has a large dipole moment of 5.2 D (20). Several BN analogues of the amino acids have been prepared, including ammoniacarhoxyborane, H,NBH,COOH, the ana logue of propionic acid, CH,CHCOOH. These compounds splay significaae physiological activity, including tumour bition and reduction of serum cholesterol. ‘The simplest unsaturated boron—nitrogen compound is ami« ‘noborane, H,NBH,, which is isoelectronic with ethene. It has, ‘only 2 transient existence in the gas phase because it readily, forms cyclic ring compounds such as a cyclohexane analogue (21). However, the aminoboranes do survive as monomers when, the double bond is shielded from reaction by bulky alkyl groups ‘on the N atom and by Cl atoms on the B atom (22). For in stance, monomeric aminoboranes can be synthesized readily by the reaction of a dialkylamine and a boron halide: © 3.8) NH ce came ce ‘The reaction also occurs with xylyl (2,4,6-trimethylphenyl) ‘groups in place of isopropyl groups. 21 NB Apart from layered boron nitride, the best known unsature ated compound of boron and nitrogen is horazine, B,NH, (23), which i isoelectronic and isostructural with benzene. Borazine was first prepared by Alfred Stock in 1926 by the reaction be- tween diborane and ammonia. Since then, many symmetrical- ly trisubstituted derivatives have heen made by procedures that depend on the protolysis of BCIbonds of BCI, by an ammonium. salt (24): 22 C,8-N(Pr P= (CH,),CH @ ana yb +380, awa ‘The use of an alkylammonium chloride yields Nealkyl substie tuted Betrichloroborazines. Bi * # i ¢ 8 ¢ c 23 Borazine, BN, 24 BNA,Despite their structural resemblance, there is little chemical ‘resemblance between borazine and benzene. Once again, the dif ference in the electronegativities of boron and nitrogen is influ- and BCI bondsin richloroborazine are much more labile than the CC. bonds in chlorobenzene. In the borazinecompound, the m electrons are concentrated on the N atoms and there is a partial positive charge on the Batoms that leaves them open to electrophilic atack. A sign of the difference is that the reaction, ‘of a chloroborazine with a Grignard reagent or hydride source ‘results in the substitution of Cl by alkyl aryl, or hydride groups. Another example of the dilference is the ready addition of HCL to borzzine to produce a trichlococyclohexane analogue (25): cr 4 yd fy od wey se actly tye hd Hea a athe ra ‘The electrophile, H', in this reaction attaches to the partially negative N atom and the nucleophile CI- attaches to the par tially positive B atom, © wnfee © e cll e 25 ENKI, EXAMPLE 13.4 Preparing borazine derivatives Give balanced chemical equations forthe synthesis of borane starting with NHC and other reagents of your choice. “Answer As we have just sen, the frst step will be the protlysis of the Cl bond in BC, by the ammonium ion. Thefore, reaction of NH,CI ‘wan wa yet NH,Cl+ 300, > #,N,0,04, + 9H ‘The Cl atoms in Bchoboratine can then be solace by dice tons from wages sch as UB, te yield borane: 3B, +1,N,8,0, "> 48,NH, #3 de 3TH BH, ete ene ete fates of NNN imettyi8,2'B"einethyborazine stating with methylamine ‘and beron tchlorise.| 13.10 Metal borides ‘Key point: Metal borides indude boron anions as isolated B atoms, lirked ceso-boron polyhedra, and hexagoral boron networks. “The ditect reaction of elemental boron and a metal at high temper atures provides a useful route to many metal horides.An example is the reaction of Ca and some other highly electropositive metals ‘with B ta produce a phase of composition MB,: Call) +6B(s) > CAB, (6) ‘Metal borides are found with a wide range of compositions, as, '8 can occur in aumerous types of structure, including isolated B atoms, chains, planar and puckered nets, and clusters. The sim= plest metal borides are metalrich compounds thar contain so lated B? ions. The most common examples of these compounds hhave the formula M,B, where M may be one of the middle to late 3d metals (Ma to Ni) in low oxidation states. Another im portant class of metal borides contains planar or puckered hex agonal nets chat have the composition MB, (Fig. 13.7). These compounds are formed primarily by electropositive metal, ine cluding magnesium, aluminium, the early d metals (fram Se t0 ‘Mn, for instance, in Period 4), and uranium (Box 13.4), ‘The boron-rich borides, typically MB, and MB,,, where M is an electropostive metal, are of even greater structural interest. In them, the B atoms link to form an intricate net~ work of interconnecting cages. In MB, compounds (which are formed by the electropostive s-block metals, such as Na, K, Ca, Se and Ba, and flock metals, the B, octahedra are linked by their vertices to form a cubic framework (Fig. 13.8). at d4n Figure 12.7 The AB, uct To give a clear gicture of the hexagonal layer B atoms outs the unit cll aw disylayed. Figure 13.8 The CaB, sructue. Not thatthe B, octahedra ae comnectes by «2 bond between vertices of adjacent 8 octahedra The cysal sa simple cube analogue of CSCI. Thus eight Ca atoms suround te cereal B, octahedron A 26 B,, cuboctahedronMagnesium diboride, Mg, is 2 cheap compound that has been known in ‘he laboratory for ver SO yeas In 2001 thissimple comgound was found to have superconducting properties (Section 24.7e). Jun Akimitsa ands co- workers discovered by chance that MgB, loses its lectical resstance when cooled tthe time, thay wore characorisng materiale used toenharce the perfomance of known hightemperature superconductors. The discovery led tw a mj ur of esearch on this new superconductor around the word In bulk materia the tanstion temperature of MgB, is 38 K and is ‘exceeded ony by the much more complicated perovskite cuprate structures (Section 24.7). The discovery ofthis latest superconductor was ever more Serendiptous than the dscover ofthe cuprate superconductors by Bednar and Miler 1885, for which they shared the Nobel Prize a year later ‘Many of the fist measurements were made using MgB, powder sraight fom the bot. Highqualty MgB, can be symhesized by heatirg fine boron and magnesium ponders together at around 950°C under pressure. Thin fils, wires, and tapes havesincebeen formed thathave potential for applications in superconducting magnets, microwave communications and power applications. ‘Magnesium dibovide has simple etuctare in which the 8 atoms are ‘aranged in gaphitlike planes wit altemating ayers of Mg atoms. The 1g atoms donate teir two valence electrons to the network of B atoms. ‘Vayingthe numberof elecrons donated to the boron conduction bands can damatcally affect the trnsition temperature. The transition temperature ofthe compaund falls if some of the Mg stoms are replaced by Aland. Increases when doged with Cu, The tansiton temperature, I, of MgB is approximately 15 K higher thar theaty predicts. This diferente hasbeen explained in terms of vibations in the latie that allow wo electrons to form a Coope pair, which then tavelsresistanceftee though the material. ‘The linked B, clusters bear a charge of —1, -2, or ~3 depend- ing on the cation with which they are associated. In the MB, ‘compounds the B-atom networks are based on linked cubocta: hedra (26) rather than the more familiar icosahedron. This type ‘of compound is formed by some of the heavier electropositive metals, particularly those ofthe f block. 13.11 Higher boranes and borohydrides Key point: The bonding in boron hydtides and polyhedral borohydride ions can be approximated by conventional 2c,2e bords together with 3c.2e bonds. In this section we describe the structures and properties of the cagerlike boranes and borohydrides, which include Stock’s se- ries BJH,,, and BH,,,.as well as the more recently discovered BH” losed polyhedra. The borohydrides have heen studied for many years as an interesting class of compounds and have found applications only recently (Box 13.5) Boron cluster compounds are best considered from the stand= point of fully delocalized molecular orbitals containing electrons hat contribute to the stability of the entire molecule. However, sometimes fruitful to identify groups of three atoms and to regard them as bonded together by versions of the 3¢,2e bonds of the kind that occur in diborane itself (1). In the more complex boranes, the three centres of the 3c,2e bonds may be BHB bridge boads, but they may also be bonds in whick three B atoms lie at the corners of an equilateral triangle with their

. This type of reaction has been used to synthesize a ‘wide ‘range of polynuclear borohydrides. "B-NMR spectros- ‘copy reveals that the boron skeleton ia [B,H,,|" consists of an icosahedron with a missing vertex (Fig. 13.13). The electrophilic displacement of H* provider a route to alkylated and halogenated species. As with Friedel~Crafts reactions, the electrophilic displacement of His catalysed bya Lewis acid, such as aluminium chloride, and the substi« tution generally occuss on the closed portion of the boron clusters: Figure 13.13 The prctondecoupled "BNMR spectrum of[8,H,]7-The ‘ido structure (a tuncatedicosahedronis indicated by the 155 patter. EXAMPLE 13.6 Proposing a structure for a boronluster reaction product Propose a stucture forthe produc ofthe reaction of BH, with LBH, in 8 refluxing polyether CH,0C,H,0CH, |which boils at 162°C) ‘Answer The prediction ofthe probable cutcome for the reactions of & boron cluster is aificult because several poducts are eften plausible and the actual outcome can be sensitive to the conitions of the action. le. the present case we note that an acidic borane, BM, is brougit into contact with the hydridic anion BH under rater vgorous conditions. Therefore, we might expect the evolution of hydrogen: 8 i, +H | 2 U8, 144,00 +, Tis et of roduc suggests the further pasty of ondersationof the etal BH, compex with [HP t id a larger borohyide. Thats Infact the coined outcome nder ese condtons oh) +RO8H, UB, +, +0 Ae turns out that, inthe presence of excess LBM, the clater building contruestogive he very stable iosheda [8,,.P" ation Ufo Hy] +[BH,] > Ui fla: B, 4,1 +34, Selttet 126 Popose 2 plasble prodict fr the reaction between {iB and ACH 13.12 Metallaboranes and carboranes key points: Maingroup and éblock metals may be incorporated into bo- ‘on hyrides through BHM bridges or more robust B~M bonds. When CH. is introduced in place of BH in a polyhedtal boron hydride, the charge of ‘the resulting carboranes ie one unit more positive; carborane anions are useful precursors of borencontaining orgenometalic compounds. Metallaboranes are metalcontaining B clusters. In some cases the metal is appended to a borohydride ion through hydrogen bridges. A more common and generally more robust group of ietallaboranes have dect metalboron bonds. An example of 4 maingroup metallahorane with an icosahedral framework ie coso-B, H, AICH,}* (31). Its prepared by interaction of the acidic hydrogens in Na,{B H,,} with time ylalums 2[B,H,,F" + AL(CH,), 2 2[B,,H,,AICH,P° + 4CH, ‘When B,H, is beated with Fe(CO), a metallated analogue of, pentahorane i formed (32). Generally boranes are quit react 31 closor(ByHyAICH,* 32 [Fe(CO),8.H4)to metal reagents and attack can occur at several points on the polyhedral cage. Therefore, reactions produce complex mixtures ‘of metallaboranes from which individual species can be isolated. Closely related to the polyhedral boranes and borohy. are the carboranes (more formally, the carbaboranes), 2 large family of clusters that contain both B and C atoms. Now we begin to see the full generality of Wade's electron counting rules, as BHT is isolectronic and isolobal with CH (33), and we can ex pect the polyhedeal borohydrides and carhoranes to be related. —- 4 One entry into the interesting and diverse world of carbo« ‘anes isthe conversion of decaborane( 14) t0 clos01,2-B,C,H,, (G4). The first reaction in this preparation is the displacement of an H, molecule from decaborane by a thioether: BH,, +2SEt, > BH, (SEt,), +H, “The loss of two H atoms in this reaction is compensated by the donation of electron pairs by the added thioethers, so the clectron count is unchanged. The product of the reaction is then converted to the carborane by the addition of an alkyne: B,,H,(SEt,), +C,H, B,,C.H,, +258, +H, ‘The fous 1 electrons of ethyne displace two thioether molecules (eo eworelsctron donors) and an H, molecule (which leaves With two additional elections). The net loss of two electrons correlates with the change in structure from a nido starting mar terial tothe close product. The C atoms are in adjacent (1,2) pox sitions, ellecting their origin fom ethyne. This closo-carhorane survives in air and can be heated without decomposition. At ‘500°C in an inert atmosphere it undergoes isomerizatien into 1,7-8,C.H,, (35), which in eurn isomerizes at 700°C to. the Li12-isomer (36). 84 close-t,2-8,,C,H,, 35 closo-1,7-B,,CH,, ‘The H atoms attached to carbon in closo-B, C,H, ate very mildly acidic, o itis possible to lithiate these compounds with Dutyllithi BCH, +2LiC,H, +B, ,C,H,Li, +2C,H,, ‘These dilithiocarboranes are good nucleophiles and undergo ‘many of the reactions characteristic of organolithium reagents 90 close 128,01, {Section 11.17). Thus, a wide range of carborane derivatives can be synthesized. For example, reaction with CO, gives a carbo- rane dicarboxylic add: BCH, Li, 24, BC.H, (COOH), Similarly, , lads to the dliodocarborane and NOCI yields B,,CH, (NO), "Although 1.2B,,C.H,, is very stable, the cluster can be par tially fragmented in strong base, and then deproconated with Nall to yield ido(B,CH, 2B,,CjHyy + 2EtO- + AEH + 28,CH, J+ 2E(OEW), + 3H, NalB,GH,,] + NaH > Na,B,GH,,] + B, The importance of these reactions is that mido-[B,CH, > (Fig. 13.14a) is an excellent ligand. In this role it mimics the ceyclopentadienyl ligand ((C,H,|"s Fig. 13.14b), which is widely used in organometallic chemistry: 2Na,[B,C,H,]+ FeCl, 2+ 2NaCl+Na,lFe(BCH,),] 2Na[C,H, ]}+ FeCl, B25 2NaCI+Fe(C,H,), Although we shall not go into the details of their synthesis, a wide range of metalcoordinated carhoranes can he synthesized. A notable feature is the of formation of multi-decker sand- wich compounds containing carborane ligands, (37) and (38). ‘The highly negative [B,CH,}~ ligand has a much greater ten= dency to form stacked sandwich compounds than the less nega tive and therefore poorer donor [CH,}"- & Pade ® a5, Pgdlbe® Hen Co &o) Figure 13.14 The islobal elation between (a) [8,(.My}™ and() [GHAI ‘The H atoms have been omitted fer catty EXAMPLE 13.7 Planning the synthesis of a carborane derivative ‘Gvebalincedchemical equationforthesythsist12-8,C,Hy(Si(CH),) Stating with decaborane(O) and other reagents o your choice “Answer We nted to ote thatthe H atoms attached to carben in oso BCH, ar very milly acidic, 0 we can Ithiate these compounds with barylthum. Weft prepare 28,6, fam decaborane: Bolg #25, > BH BAL), Hy gH BR) #GH, > BCH +2, +H, ‘The product is then lithiated by lithium aly, where the alkyl carbanion abstracts the slightly acidic hydrogen atoms om BCH, replacing them with i BG +2, BLGHAL +2, ‘The resulting carbone is then used in a nucleophilic displaremert on ‘(CH 10 eld th desied product B.CoHli, +2 SICH,), Cl B.C,H(S(CH,)), +2 UCL Selétest 137 Propose a syntheis for the polymer precusor Sy Hef SECH,)CD, fom 123M, andotherreagens of our choice. Key points: LiAIH, and LiGAH, ae useful pecursers of MH,L, complexes; LUAIH, i also used asa source of H™ ions in the preparation of metaloid Inytides, such as Sik, The alky aluminium hydrides ae used to couple alkenes. Aluminium hydride, AIH,, is a polymeric solid. The allylalue ‘minium hydrides, such as AL(C.H,).H,, are well-known mo- lecular compounds and contain Al-H-Al 3e,2e bonds (Section 2.11), Hydrides of this kind are used to couple alkenes, the tial step being the addition of the AIH entity across the C=C double bond, as in hydroboration (Section 13.6c). Pure Ga,H, has been prepared only relatively recently but derivatives have Iheen Kknawn for some time. The hydrides of indium and thale lium ae very unstable. ‘The metathesis of the halides with LiHt leads to lithium tetahydridosluminate, LiAIH,, oF the analogous LiGaH 4LH+ EC, LiBH, +3111 (E= ALGa) ‘The direct reaction of Li, Al, and H, leads to the formation of either LiAIH, or 1i,AIH,, depending on the conditions of the reaction. Theit formal analogy with halide complexes such as AICI; and AIFF should be noted. ‘The AIH; and GaH; ions are tetrshedral, and are much more hnydridic chan BH. Theis hydridic character is consistent wih the higher clectronegativity of B compared with Aland Ga and the fact tht BH is more covalent than AIH; and GaH. For example, NaAIH, reacts violently with water but, as we saw earlier basic aqueous solutions of NaBH, are useful in synthe chemistry. They are also much stronger reducing agents; LiAH, is commercially available and widely used as a strong hydride source and as a reducing agent. ‘With the halides of many nonmetallic elements, AIH; serves asa hydride source in metthess reactions, such as the faction of lithium teteahydridoaluminate with slicon tetrachloride in tetzahydrofuran solution t preduce silane: LIAIH, + SiC, 2 Lialcl, + Siri, ‘The general cule in this important type of reaction is that H~ ‘migrates from the element of lower electronegativity (Al in the example) to the element of greater electronegativty (Si). Under conditions of controlled protolysis, both AIH; and Cal; lead to complexes of aluminium of gallium hydride: LEH, +[(CH,), NHICI > (CH,), N—EH, +LiCl+H, (=A, Ga} In striking contrast ro BH, complexes, these complexes will add second molecule of base to form fivecoordinate complexes of aluminium of gallium hydeide: (CH,),N-EH, + N(CH,), > (CH,)N),EH, (E=Al,Ga) ‘This behaviour is consistent with the trend for Period 3 and heavier p-block elements to form five- and six-coordinate hyper valent compounds (Section 2.6b). 13.14 Trihalides of aluminium, gallium, indium, and thallium ‘Key points: Aluminium, gallium, and indium all favour the +3 oxidation sate, and their tahalides are Lewis acids. ‘wihalides are less ‘able than those ofits cogeners. Although direct reaction of Al, Ga, or In with a halogen yields a halide, these electropositive mecals also react with HCl or HBr 2s, and the latter is usually a more convenient route: 2Alls)+6HC(g) 2292 AICI, 6) + 3H) AIF, and GaF, form salts of the type Na,AIF, (cryolite) and 1Na,GaF., which contain octahedral [MF.J*" complex iors. Cxy= lite occurs naturally and molten syathetic cryolit is used as a solvent for bausite in the industrial extraction of aluminium. ‘The Lewis acidities of the trihalides reflect the relative chemic cal hardness of the Group 13 elements. Thus, towards a hard Lewis base (such as ethyl acetate, which is hard because of its 0 donor atoms), the Lewis acidities of the halides weaken as the softness of the acceptor element increases, so the Lewis acidites, fallin the order: BCI, > AICI, > GaCl,