/ SOME PROPERTIES OF THALLIUM(), 373 Cement ‘Aluminium compounds, particularly tricalcium aluminate CasAl,O,, are very important as constituents of Portland and high alumina cements. The formula of tricalcium aluminate is better written Cao[AlsOis], because it contains 12-membered rings of Si—O—Si—O made by joining six AlO, tetrahedra, Portland cement is made by heating the correct mixture of limestone (CaCO) with sand (SiO) and clay (aluminosilicate) at a temperature of 1450-1600°C in a rotary kiln. When mixed with sand and water Portland cement sets to give concrete, a hard whitish insoluble solid, similar in appearance to Portland stone. (Portland stone is limestone quarried on Portland Bill in Dorset, England.) Between 2% and 5% of gypsum CaSO, 2H,0 is added to slow down the setting process, as slow setting greatly increases the strength. The composition of cement is usually given in terms of the oxides. A typical composition for Portland cement is CaO 70%, SiOz 20%, Al,O3 5%, Fe,O3 3%, CaSO,-2H20 2%. Total world production of cement was 1396 million tonnes in 1993, about 70% of which was Portland cement. High alumina cement is made by fusing limestone and bauxite with small amounts of SiO, and TiO, at 1400-1500°C in either an open hearth furnace or a rotary kiln. High alumina cement is more expensive than is Portland cement, but has one major advantage over Portland cement — it sets much quicker and develops high strength within one day. It is used to make beams for bridges and buildings. High alumina cement has good resistance to sea water and dilute mineral acids. It withstands temperatures up to 1500°C and so may be used with refractory bricks in furnaces. A typical analysis of high alumina cement is CaO 40%, Al,O3 40%, SiOz 10%, Fe203 10%. There has been much publicity over structural failures of beams made of high alumina cement. Failure ts due to prolonged exposure to hot wet conditions, or using too much water when mixing the sand and cement. This latter results in it setting too quickly and thus not having time to crystallize properly. Reactions of Ga, In and TI Gallium and indium are stable in air and are not attacked by water unless free oxygen is present. Thallium is a little more reactive and is superficially oxidized by air. All three metals dissolve in dilute acids, liberating hydro- gen. Gallium is amphoteric like aluminium, and it dissolves in aqueous NaOH, liberating H, and forming gallates. The oxides and hydroxides of Al and Ga are also amphoteric. In contrast, the oxides and hydroxides of In and Ti are purely basic, All three metals react with the halogens on gentle warming. SOME PROPERTIES OF THALLIUM(I) Tralium(t) or thallous compounds are well known. They are typically ‘Olourless. They are also extremely poisonous. When ingested, traces turn[| ___— rr ecans ———} ‘he har very black, bt argc doses anes of ai ad death They are tori bensuse they upset the enzyme stems lathe body. i aqueous solution the TI fn fs mach more table hon TAIN 13S lonie fads of TI" (LS0A) jp between that of K" (138A}"and Rb" (2A). For this teason 11 resembles Gro 1 one amber of sea TIOH and 740 are bot soluble in water, aad are strony basse ‘Tey absorb CO: fom the a, forming TCO. The stub of mow of the at aight Tower than for potassium sls TI” can ease Rein sme enzymes, and can ths Be seed ae bsg trace the body. “There are some diferences. TIOH i yefow, and on Heating 1 100°C turns ito back 1,0. Toe coordination number of "Is wal o 8 spared wth 6 for Group 1 fons. TFs soluble Sa water, bt the whet Ilids ace almon ieouble. There Is seo some silty mth Ag at "TiChisseastve to ight. lt darkens when exposed right rather ke Ag, but TICK nat seuble ie NHOH whist AGCI is solube (COMPOUNDS OF BORON AND OXYGEN Boronseqsionide and thebortes “These are the mest important compounds of boron, Sesul meant one and 1 hall, 0 the onde shoud have a orala MOyy, of Os. Al he lemens inthe prop form sesqulondes when heated i Cony, BOs ‘Sade more convene by dehyegting bread 1480, nao," 3,0, B04 is a pica nonmeatieosde aod is aii ints prope tis the anbyiideofhobors ned std t reacts with Basi (etal) iden, forming at calle borates or metaborates Inthe bara bead tet, BOs Crborts Nag{8,0o{0H)]-8H,0 fe hentedin a Buptn burner fame with ‘metal onder ona oop of platinum wire, The mite foes to gre 9 pas Ike metaborate bead. Metaorate beads of many vars reas pave charctenstc colours, nd so tht reaction povides 9 men of ftuog ‘he metal. This somple test proded the fst prot tat wisn Be fontaine’ cova. 600 + B.0,——- Co(B0.)2 However is posable to force ByO, to behave asa base oride by reacting wit very strongly acdc compounds. TRS With PO, oF AsO, ‘boron phosphate or boron arsenate are oumed. =, 2,0, + 7,0, 2090, aeCOMPOUNDS OF BORON AND OXYGEN 375, Orthoboric acid HyBOs is soluble in water, and behaves as a weak monobasic acid. It does’ not donate protons like most acids, but rather it accepts OH™. Itis therefore a Lewis acid, and is better written as B(OH)s. B(OH); + 2H2O = H30* + [B(OH),]” pK = 9.25 [H;BO3] OH HO OH]~ | SZ B B /\ _ HO OH HO OH plane triangle tetrahedral metaborate ion Polymeric metaborate species are formed at higher concentrations, for example: 3B(OH); = H;0* + [B;03(OH).J” + H20 pK = 6.84 {3H;B03] HO - \ B—O OH J N\¢ ° B \O Os N BH OH / HO Acidic properties of HBO or B(OH); Since B(OH); only partially reacts with water to form H,O* and {B(OH).J”, it behaves as a weak acid. Thus H3BO3 or (B(OH)5) cannot be titrated satisfactorily with NaOH, as a sharp end point is not obtained. If certain organic polyhydroxy compounds such as glycerol, mannitol or sugars are added to the titration mixture, then B(OH), behaves as a strong monobasic acid, It can now be titrated with NaOH, and the end point ate using phenolphthalein as indicator (indicator changes at pH B(OH); + NaOH = Na[B(OH),] NaBO, + 2H,0 sodium metaborate The added compound must be a cis-diol, to enhance the acidic properties in this way. (This means that it has OH groups on adjacent carbon atoms in the cis configuration.) The cis-diol forms very stable complexes with the(gr anes {BCOHpd~ formed bythe forward reaction above, thus effectively teow Ing from solution The reacon i everuble Thus femora of one of the produce athe ght hand sie ofthe equation upsets the blanc, andthe feacton proeeds completely tothe right Thus al the B(O¥Dyeeaet ath NAOH ip effect w sce ss srong sedi the presence ofthe cs dol I i Con [HO ony Hot Srucuresofborates In the simple borates exch B atom bonded 10 Uree oxygen stom, seanged a the corset ofan equstecal tangle Ths would be predted ftom the orbs shed for bonding sue.. & ote GO EEO snp eps a as ‘eben sro Fee ang myocar “Thus orhobone ad eoetnns tangle BO} unite Inthe sold the [B(OH)s units sre hydrogen bonded together mo twordmensona sheets ‘mh almost hexagonal spametry (See Figure 123) The layer are qe lavge distance apart (38), and han crystal Deak quite exe ‘ety ne pate At one time other sed wa ed gw ly nt Septic tskum powder for babes, beau forme a fine powder 1820 longer used we Sometimes exined 9 ea “The ornobartes conti dacete BOY vont. and examles sateCOMPOUNDS OF BORON AND OXYGEN 377 Figure 12.3 Hydrogen bonded structure of orthoboric acid. Mg,(BO:), and the lanthanide orthoborates Ln™BOs. In the metaborates simple units (BOs planar triangular units or BO, tetrahedra) join together to form a variety of polymeric chain and ring structures (see Figure 12.4). Thus two triangular units join by sharing one corner in Mg,[BzOs] and Co!'[B,0.]. These are called pyroborates by analogy with pyrophosphates. Three triangular units share corners and form a ring in sodium and potassium metaborates NaBO, and KBO, (Figure 12.4b) which are better written Nas{BO¢] and K3[B3O.]. Many triangular units may polymerize i an infinite chain, e.g. as calcium metaborate [Ca(BO )2], (Figure 4a). Ina similar way discrete tetrahedral units are found in Na;[B(OH),]CI and TaYBO,. Two tetrahedra may join by sharing one corner, as in Me[(HO);B - O- B(OH)s]. Other structures form rings, chains, sheets and three-dimensional polymers. Some interesting structures including both triangular and tetrahedral units are formed when polymerization occurs. The spiro compound K[B;0,(OH),] (Figure 12.4c) contains one tetrahedral unit and four triangular units. Borax is usually written as Na2B,O;- 10HO but is actually made from two tetrahedra and two triangular units joined as shown (Figure 12.4) and should be written Na,[B,Os(OH),] - 8H20. Borax The most common metaborate is borax Na;[B,Os(OH),]-8H,0. It is a Useful primary standard for titrating against acids.fj or eS) pay 124 Srcues of sme boas (2) Metborate chan [Cx{BO9 made Hoy ome) Cones mente MgO eed ey ans ‘nade op of for angst BO, unas and one tetrahedral BO, wet (@) Borat (Bi O 01 SG) made up of to tanga vo teat ass ‘istone{PsOKOH andthe ier warms ected (28,0014 81,0) + 2HCt—+ 2N4CI + 41,00, + 51,0 (One ofthe products Hf10 tel a weak send Ths the indicator ied to detec the ed pow of th reaction must be one tht ws Uraffested by HyHOs ‘Metiy! orange 1s normaly wsed, whch changes im the pit range 31-44 ‘One mle of borax eats witht moles of aed ‘Thi is Deca when tras dsoved in water bor B(OH) and [B(OH are formed, bat only the (B(OH) teat wath HCLCL COMPOUNDS OF BORON AND OXYGEN 379 {B,0,(OH),)°" + SH,0 = 2B(OH); + 2[B(OH)«]~ 2{B(OH).|” + 2H,0* > 2B(OH); + 44,0 The last reaction will titrate at pH 9.2, so the indicator must have pK, < ca. 8. Borax is also used as a buffer since its aqueous solution contains equal amounts of weak acid and its salt. Sodium peroxoborate Large amounts of sodium peroxoborate are produced, and world produc- tion is about 550000 tonnes/year. There are two main preparative methods:, 1. Electrolysis of a solution of sodium borate (containing some NazCO3). 2. By oxidizing boric acid or sodium metaborate with hydrogen peroxide. 2NaBO; + 2H,O, + 6H,0 > Na,[(OH),B(O—O),B(OH),] -6H,O0 sodium petborte sodium peroxoborate HO] 0-0, | Oa \/ 7 B B 7 \ 7X HO 0-0 OH peroxoborate fon Sodium peroxoborate, is used as a brightener in washing powders. It is compatible with enzymes which are added to some ‘biological’ powders. In very hot water (over 80°C) the peroxide linkages O—O break down to give H,02. Isopolyacids of B, Si and P Other elements form polymeric compounds similar to the borates; notably Si forms silicates and P forms phosphates. These polymeric compounds are called .isopolyacids. (The name isopolyacid means that acidic ions are polymerized together: Iso means ‘the same’, and indicates that only one type of ion is involved. If two different types of ion polymerize together, for example phosphate and molybdate ions, the phosphomolybdate polymer is called a heteropolyacid.) The principles underlying the structures of borates have been set out by Christ and Clark (see Further Reading). Thi inci summarized as follows: ee aeeaana 1.°B often forms triangular’ BO units. Sometimes these remain mono- iMeric, but they may form polynuclear ions by sharing the O atoms at Corners, This links the triangular units together into chains, rings and 3 two-dimensional flat sheet-like structures . ee forms tetrahedral BO, units. More complex polynuclear ies ntain both triangular BOs units and tetrahedral BO, units ‘ed together by sharing corners. These structures are not flat.wal 7a GROUP ELEMENTS) 3 Hydrated borates may accep protons. These se added the folowing der) O" 107s ae converted to OH, (1) tetabeial O ate frotnsted, (nthe O in plana angles are protonated and (9) an) Fee OH groups are converted to 1,0. 4 Hygeate borates may polymerize by ehevnating HO. This may be {oles by bresking or tearanging =O bonds 5 "ABO. atten ex nthe prevence of more complex polation “Tse polymere borat structures tend t beak up when doe an Tn cots, the tutus of phosphates and iicates ae alway based on tetahedsl PO, and SiO, unis The trae may polymere 9 ‘hans ag and hre-dimcrsonal stuetures These suucires ae het tmore tube ed Jo not bre up an sltion ‘Qualtateanayss of boron compounds ‘When bocates are treated wth HF (or wath concentrated $0, and CAF) the volatile compound BF, 1s formed I the BE, as produced i tr ‘duced no 2 fame (or example a Bunsen fame) the flome ges a ee setensue ree coloration cone H,SO, + CaF; + 2HF + C390, HBO, + 3HF-— 20F; + 340 ‘An alternative tes 19 make the eter methyl borate (OCH) The fuspected borate tarmple ie med with concentrated WSO, 0 form H\BOs. and warmed wih met aloo! mall evaporating basin B(OH) + SCHON BOCK): + 34,0 “The concentrated H.S0, removes the wae formed ‘The mature then feton fre Methyl borate ela, and colour the fe pees Fuobonssed xB dsolves im aqueous HF, forming fuobone sed HBF, 1yB0, + SHIP HP + (BFaf° + 3140 Fivobone aod strong ad. and commercial slatons contain 4% se ‘The [BF] tons tetahedal and igoborates resem peehlorates 10; and sulphates m crystal structure and slaty (KIO, and KBP, ae both ‘ot very soluble water) The (BF,)” and (C104) tons havea very ow {endeny to form complexes in aqueous olation, though few eorepleses ‘reformed im non-aqueosn meds Bondes “Thote ae over 200 binary compounds between metak and boron These ie many diferent simchometnes ‘The mow common are MB. MBEL THE OTHER GROUP 13 OXIDES 381 MB,, MB, and MB,, though formulae as diverse as MsB and MBgg, are known, Some of the compounds are nonstoichiometric. The formulae of some of the compounds cannot be rationalized by the application of simple valency rules, and are best explained by multi-centre bonding. ; They may be prepared by heating the metal with boron, and by a variety of other methods. The metal-rich borides are mostly with transition metals. fivey are hard, and have very high melting points: ZrBz, HfB, NDB, and TaB» all melt over 3000°C. The melting points and the electrical con- ductivities are often higher than for the parent metals. Thus TiB2 conducts five times as well as Ti metal. Borides are often chemically inert, and they have several us . Boron carbide is commonly written as B,C. It is produced in quantities of tonnes by reducing BO, with C at 1600°C. It is a useful source of B, and is also used as an abrasive for polishing. It is used in brake linings for cars, Fibres of B,C have an enormous tensile strength, and are used to make bullet-proof clothing. These fibres are made as follows: GH 4 ABC) ¢ Cee es BC HCl Boron carbide should be written B,;C., but its composition varies and may approach B,C). The structure comprises a series of B,2 icosahedra. Each icosahedron is linked to six others through either four B—C—B linkages and two B—B linkages, or through six B—C—B linkages, The structure is a cluster compound, and can only be explained by multi- centre bondin Powder fabrication techniques are used to fabricate parts such as turbine blades and rocket nozzles from powdered borides such as CrB2, TiB2, and ZrB., Boron stee! is used in the nuclear industry for’shielding and for control rods in reactors because '’B has a very high absorption cross-section for thermal neutrons. x + THE OTHER GROUP 13 OXIDES Alumina Al,O; exists principally in two crystalline forms called a-Al,O3 or corundum, and y-Al,O3, and in addition there is a fibrous form which is made commercially. Corundum is found as a mineral, and a-Al,O; is also made by heating AW(OH), or y-Al,O, above 1000°C. Corundum is extremely hard (9 on Moh’s scale) and is used as ‘jewellers’ rouge’ to polish glass. (See Appendix N). An impure form of corundum. contaminated with iron oxide and silica. is called emery. This is used to make emery paper Csandpaper’ used to-polish metals). Corundum 1s unaffected by acids. It hay a high melting point of over 2000°C. It is used as a refractory to line furnaces and to make containers for high temperature reactions. The crystal structure of corundum is hexagonally close-packed oxygen atoms, With two thirds of the octahedral holes filled by AL* ions.Ge] Car eas ALO, w made by dehydeatng ANOH), below 480°C and mon tras toe ANOy a daslves im aoe absobe water and 1 ted for shronategraphy Fibrous ALOy 1s made commercially by (Ct and Du Foot Fibres bf ‘ALO, ond (210%) st sold under the ade name Saf "These fre fel ie skate 2-Sens 1 length and ae 120) the dzmetor of s ham hair ‘The fibres are halow and ate fexble thoogh they have 2 hgh fennle strength tn addivon they are chem ert and wth pro longed heating vp to, UO0°C The Aes can be woven vito rope o¢ {Sie and are ao wed for making chemi use paper aad suppor for cata Fbrer ae ls weed to strengthen certnn metas (Mg AL fant Po) for ceample. Al reiforced by SOs fee Ge tes ser han pore Al Fibes ako have excelent thermal snd elects insulting, Proper “Alumina white but con be coloured by the addon of COs or FeO, Wont sapphires ae gem qual corundum Syetetrbvescanbe ‘made by stony heating s matte of Ay and CO, forexdme 90 ‘ny hyglogen lame’ Rulves ate very had and ae used for Jeneley and tomakehesnngs in watches and instrument ‘Ths aby ined ene Blue sapphires ave another med ox containing ence of Fe” Fe™™ nT" The mineral spinel MpANOy another moted ode Te pes ‘me tothe stuctre adopted by many MMO, compounds ‘Mur hab aver song aint lor oygen The entaly fora ‘ven of ALOy 6 ~16TOLI mal" gher (wore negave) tha for prac ily a otber mete oxides "Ths Almay be sed the themat eductod ‘fies stable tal ides MnO, + BAL=> 4ALOs + 9M (Qusteaue seayen of lama . In qltatwe amass: AMOH), ws preciptated as a white gelstpous substance hen NH\OH i aided to he solaion (aler prewausty Femorg sad insoluble sulphides wh HS) Fe(OH), COM), and Za(Oth: ate ko precited. but Fe(OH) 6 brown CH(OW)y grey ‘cen of grey-blue Z(H); white hike AIOH), bot i not gla tious. Zn(O) solves m excess LOH ‘bores NOH), doesn ‘A consrmatory tet for alumaman the formation of rd pepste ftom AI(OH) a the de alaminon Amphoten behaviour —alumamates 2 ANOH), ss amphotene 1 rests pica af nase ve reacts wh ‘5s fore ats tit cota the [AI(HsO}4* on, However ANCOHs Sows Some sede properties when danse» NSOH forming sodium alamanate (However, ANOH), 1s reprecytated by the adivon of exon ‘onde showing that he sade properes are wey weak)TETRAHYDRIDOBORATES (BOROHYDRIDES) Al(OH); 2228 NaAl(OH). sodum NaAlO,+2H,O _ aamnate The formula of aluminates is often written as NaAlO2 -2H20 (which is equivalent to [Al(OH)4]~). Raman spectra suggest that the structure of the aluminate ion is more complicated than this implies, and the structure changes with both pH and concentration: . Between pH 8 and 12 the ions polymerize using OH bridges and each aluminium is octahedrally coordinated. In dilute solutions above pH values of 13, a tetrahedral [A(OH),J~ ion exists. In concentrated solutions above 1.5M and at pH values greater than 13 the ion exists as a dimer: [(HO);Al—O—AI(OH)5]>— Ga,03 and Ga(OH); are both amphoteric like the corresponding Al compounds. Ga(OH), is white and gelatinous and dissolves in alkali, forming gallates. Tl,O3 and In, are completely basic, and form neither hydrates nor hydroxides. In contrast, thallous hydroxide TIOH is a strong base, and is soluble in water. Thus TIOH differs from the trivalent hydroxides and resembles the Group 1 hydroxides. Where an element can exist in more than one valency state, there is a general tendency for the lowest valency state to be the most basic. - Thallium(II1) acetate and trifluoroacetate can be made by dissolving the oxide in the appropriate acid. They are used in the synthesis of organo- metallic thallium compounds. ’ ‘ PoYN TETRAHYDRIDOBORATES (BOROHYDRIDES) Stable complexes containing the group [BH,|~ are well known. These should be called tetrahydridoborates, though the old name borohydride is still widely used. The tetrahydridoborate ion [BH,]” is tetrahedral, and the sodium salt Na[BH,] is the most important compound. It is usually Prepared from trimethylborate. It is ionic, and has a sodium chloride structure. 4B(OMe), + 4NaH SUC Neh neu, Nal BH,] + 3Na[B(OMe),] tumethylborate tetrahydrofuran solvent Other tetrahydridoborates are made by treating Na[BH,] with the appro- Priate metal chloride. The alkali metal tetrahydridoborates are white ionic solids and react with water with varying ease. Thus Li[BH,] reacts violently with water, but Na[BH,] may be recrystallized from cold water with only Slight decomposition, and K{BH4] is quite stable. Li[BH,] + 2H,O > LiBO, + 4H, The alkali metal tetrahydridoborates are valuable reducing agents in both Mmorganic and organic chemistry. Na[BH,] is stable in alcoholic and | [383Lr —r—C gveous solutions This makes usfl reagent for reducing aldehydes to frmay scools, and ketnes to Secondary aleahol Iti 4 mileage agent, and atcks ses of tow electron deny Thus otet fonchoya _roupr such as C=C, COOH and NO, ae ot romalyatacke? B CHOMPELR CHLOH — pumary aconot R R Neco min, ‘c=0 MH, \cHOH —scoondtysleahal / ee Not ll ttahydndoborates are onic The Benim, aluminum and resto metal borohydnides become incresnly covet an wat Te these the [BH group acts as ged safes covalent compounds ‘wkmetsiens Oner more Hatomsin 2 [BH,]- act aa bide an bond to the metal, forming 2 thee-centre bond with two electrons shared by hand unsos that st ma orm ene, Wo cents hon tothe mtalion ‘Tes He(HEy) ABH 2nd Ze (BH) ae covalent, ad reset strongly wath water Inthe Aland Z? ‘ampounds, each BH; foams two hydrogen badges, whist the Be ‘ompoond two of the thee BH form thes hydrogen bndges gure 12§ Sracne of ALDI) an Be(BHLy (Aer. Ents and A, [Ship Alar dips f Toop Chamay, Srey Ty Rowe a Kegsa rat) “Te ater clement the group so form elecrotdefnent hyddet (Alig ara white mvolabiesold [eeu redosing agent and resco” Soh tater His extenswelypolmeraed by Sexntr byarogen badges 2 Tero those borane (Te statue of @ AIH s know and each Al prerptes ma brides). Aluouavm hyders best made rom L(A] Exdaleh Itcan temade from Lil sed AN, ether soliton, but a ‘sees LH Inu slamsnam tydade LAG) formed send[ TRIHALIDES 385 LiH + AICI; > (AIH), “> Li[AIH,] ‘Li[AIHL,] is 4 most useful organic reducing agent because it will reduce functional groups, but in general it does not attack double bonds. It is analogous to the borohydrides but cannot be used in aqueous solutions. Gallium forms compounds analogous to the borohydrides, e.g. Li[GaF]. Indium forms a polymeric hydride (InH),,, but there is some doubt about the existence of a hydride of thallium. TRIHALIDES All the elements form trihalides. The boron halides are covalent. BF; is gaseous, BCI; liquid and BI; is solid. BF; is by far the most important. It is a colourless gas, boiling point —101°C, and is made in large quantities: B,03 + 3CaF) + conc, 3H,SO,““»2BF; + 3CaSO, + 3H20 B,O, + 6NH,BF, “+ 8BF; + 6NH3 + 3H,0 Both BF; gas and its complex with diethyl ether (C;Hs),0 + BF (a viscous liquid) are commercially available. The shape of the BF; molecule is a planar triangle with bond angles of 120°, This is predicted by VSEPR theory as the most stable shape for three outer electron pairs round B. The valence bond theory also predicts 4 planar triangle with hybridization of one s and two p orbitals used for bonding. However, the B atom only has six electrons in its outer shell and this is termed electron deficient. Electronic structure of is 2s ee boron atom—excited state [ru] ft + |t ay three singly occupied orbitals form bonds with unpaired electrons from three halogen atoms — shape plane triangle (sp? hybridization) ‘The bond lengths in BF; are 1.30 A, and are significantly shorter than the sum of the covalent radii (B = 0.80A, F = 0.72A). The bond energy is very high: 646k mol™!, which is higher than for any single bond. The shortness and strength of the bonds is interpreted in terms of a px—pr interaction, that is the bonds possess some double bond character. The empty 2p; atomic orbital on B which is not involved in hybridization is Perpendicular to the triangle containing the sp? hybrid orbitals. This pz oo Tay accept an electron pair from a full p, orbital on any one of the es fluorine atoms. Thus a dative m bond is formed, and the B atom ains an octet of electrons. If one localized double bond existed, thenthere wontd be one short bond and two longer ones However al ess: trements bow thatthe thro Bond length are wena! The old vale bond explsnavon ef fhe was reronance between the crest ‘he double ond a deren postions “be modern explanation tha be ‘oubte bonds eetoaiaed The four p, atone otbtals fom B andthe three F stom form a fourcenirem molecular onal covering al foot soms whl sont two bonding eleronsDeloalued x bonding is ‘decebed more fly mt Chapter © pre 126 State of BFS “The empty 2p, salon the boron stom wn BFy can abo be filed by | lone para lion fom donor molecules sch 5 1,0, NH, (CH ory rns suchas F- When ths Ours tetrahedral molecole Or 0018 formed Fo 0k FON, FONMe fr FY Vv Ve \ 0 \e io 8 8 ry ss. /\, /\, x eee ee ree Ye, (Once erated complex hasbeen formed, the possblay for x bonding solongerensts In HyN > BF, the BF dsiances 38, and ip MeN 2 BFs the datance 139A, touch longer than the 130A By Since ‘he boton bes wl Seep clctron pats fm urserous som ad ot buch ac F-, 0, Ny P and 8, they af seg a tong Lev acs “Thetnbslde ar prt nutoal cemvee,poreulaty BF ado a ewer extent BCI, They ae wed to prepare elemental boron They ae Sts very wel for promod certain organcreschons Insome canes BF, 15 ured up m the reaction. and in others at asa catlyt by foro BE, complex wth ope or both reactants Forming antennae com pound nthe way Toweis the acnation energy Examples meade 1 Faedel-Crattseactions suchas alglauons and cauons Tn these the 1B, wad up m fe Fetcon, and 9 emt sly eatlyte GH, + GALE + BE, Gilly GH + HT + (BEG) 2 Wecte as a catayat 9 several rescuons sed + alcohol eter + water ‘benene + leone» ayibenzene + water{ . TRIHALIDES 387 3, Considerable quantities of BF3 are also used as a polymerization ‘catalyst in the production of polyisobutenes (used to: make viscostatic -Jubricating ils), coumarone~indene resins, and butadiene~styrene rubbers. : ‘About 4000 tonnes a year of BF; are produced in the USA from B20; or borak: “B,O; + 6HE + 3H,SO, > 2BF; + 3H,SO,-H,O Na,[B,Os(OH),} + 12HF 8S [Na,O(BF;).] 4BF; + 2NaHSP, + Ho Os The boron halides are all hydrolysed by water. BF; hydrolyses incom: pletely and forms fluoborates. This is because the HF first formed reacts with the H3BO3. 4BF; + 12H2O — 4H3BO; + 12HF 12HF + 3H3BO; > 3H* + 3[BF,]~ + 9H.O 4BF; + 3H,O > H;BO; + 3H* + 3[BF,] The other halides hydrolyse completely, giving boric acid. BCh + 3H,0 > HBO; + 3HC! The fluorides of Al, Ga, In and TI are torjic and have high melting points. The other halides are largely covalent when anhydrous. AICI, AIBr; and GaCl; exist as dimers, thus attaining an octet of electrons. The dimeric formula is'retained when the halides dissolve in non-polar solvents such as benzene. However, when the halides dissolve in water, the high enthalpy of hydration is sufficient to break the covalent dimer into (M-6H,0}+ and 3X~ ions. At low temperatures AICI; exists as a close packed lattice of Cl- with A+ occupying octahedral holes. On heating AlzCla species are formed and the volume of the solid greatly increases. This oe how, close the bonding in this compound is to the ionic/covalent order, ,Group 13 elements have only three. valency electrons., When these are used to form three covalent bonds, the atom has a share in only six electrons, The compounds are therefore electron deficient. The BX3 halides attain an octet by x bonding. The other elements in the group have larger atoms and cannot get effective x overlap, so they polymerize to Femedy the electron deficiency. AICI; is an important industrial chemical. Production is about 25000 tonnes/year in the USA alone. Anhydrous AICI; (and to a lesser extent AIBr,) is used as the ‘catalyst’ in a variety of Friedel-Crafts type of Teactions for alkylations and acylations. Large amounts of ethylbenzene are made in this way and are used to make styrene. (Polystyrene produc- tion was 8.2 million tonnes in 1991.) a oc NN a ‘al Al BAN Figure 12.7 Structure of dimer. cl Soe 4 cl ca Non-eclipsed ch ch N Zz | oe! || AA. Nat Planar Boron dichtondewate econ OO hows, Sisto tts Brats Fegus 1H) Catly HF CHYCH,CI + AIC Gale CHCHY + HY + faNCU “Tot nat tue ‘cataly" action 38 the AICI sed 9p athe formation ‘Of[Alch]” oF [AlBrs1 s8 sent pr ofthe reason Acyatons ae Gay HREOC + AICI + COG, +H + [ACY [AlCl 6a wie to eataye the reaction to make ety bromide (whch ted vo make the petrol adda POEL) CH=CH, + HB cyte AIG) 16 alo weed mn the manulactare of anthraqsinone (seed nthe yet nduty) and ddeeybensene (ede eke detergents), and ‘the womermton of hydoeafbons (geileur snd) Tiyan unuwval compound Tes somorphous with Cay and NHL ndconsins the ines odie ony Ths the metal present 515 the oxidation state (#1) not (Il) DINALIDES Boron fos hse of formals BaXs Thee deconpoteHowly arom temperate By, can be made 2 flows 2801+ atte AEM + Hcl “Thece free raion about the BB bond and in he gxteous and hgusd states the molecule adopts a aon ecpsed conformation I he ld ate fhe molecules plonar becouse of ext forces abd ease of packing {Gator and vedo sto form "ikahder see diagram on page 367 Gad + Ga 26801, I+ Hci 2incl, “Those are sore propety wasten Ga°IGaCu) and Ta°(inC)- and conta MII) and MHD rather than Ga(H) and Tat) MONOMALIDES ‘Boros forms ever stable pole monotaies (BX), pc” i B.C B.C BCL BuChe Buy BrCl ‘The compounds B,C, B,Clq and ByCl re erysatine sells andthe{ DIFFERENCES BETWEEN BORON AND THE OTHER ELEMENTS 389 structures (Figure 12.8) have a closed cage or polyhedron of B atoms, ‘here each B atom is bonded to three other B atoms and to one Cl atom. Since B has only three valency electrons there are not enough electrons to form normal electron pair bonds. It is probable that multi-centre & bonds cover all the B atoms in the cage. ‘Al, Ga and In all form monohalides MX in the gas phase at elevated temperatures, ¢.g. AIGK 2A ete SAIC temperature ‘These compounds are not very stable, and are covalent. Thallium forms univalent thallous halides which are more stable th ~ the thallium trihalides. This illustrates the inert pair effect, and TIF is ionic. COMPLEXES Group 13 elements form complexes much more readily than the s-block elements, because of their smaller size and increased charge. Tetrahedral hydride and halide complexes such as Li[AIH,] and H[BF.] have al- ready been mentioned. In addition many octahedral complexes such as {GaCl,~, [InCi.}>- and [TICI®~ are known. The most important octahedral complexes are those with chelate groups, for example B- diketones such as acetylacetone, oxalate ions, dicarboxylic acids, pyro- catechol, and also 8-hydroxyquinoline. (See Figure 12.9.) The latter complex has been used in the gravimetric determination of aluminium. DIFFERENCES BETWEEN BORON AND THE OTHER ELEMENTS Boron differs significantly from the other elements in Group 13, mainly because the atoms are very small. It is always covalent, and it is non- metallic. In addition, boron shows a diagonal relationship with silicon in Group 14. 1, BOs is an acidic oxide; like SiO. This is in contrast to Al,03, which is amphoteric. H3BO3, which may be written B(OH),, is acidic, whilst Al(OH); is amphoteric. Simple borates and silicate ions can polymerize, forming isopolyacids. Both are built on similar structural principles, namely by sharing oxygen atoms. Complicated chains, rings, sheets and other structures are formed in this way. Aluminium forms no analogous compounds. . The hydrides of B are gaseous, readily hydrolysed and spontaneously in- flammable. In contrast aluminium hydride is a polymeric solid (AIHa)q. SiH, is gaseous, readily hydrolysed and inflammable. Apart from BF;, the halides of B and Si hydrolyse readily and vig- Crously. The aluminium halides are only partly hydrolysed in water. re 3. SH, o—c, \, Mi H / =C. 4 acetyl aor soe : on .29 Me 0 So| 3 oxalate complex i Aw 3 8 hydroxyquinotine complex. Figure 12.9 Some complexBORON HYDRIDES ‘Compounds known "None of the Group 13 elements react ety wh bySrogen but sevéat Interesting Ryder are Know "The boron dade ce sorteine alled borane by analog) wi the lkates (hjurocaebors) Almost 20 branes Inve Been reported, and IL are well careterned| ‘They fl wt two 1 Dados (called mado boranes) 2 Ales! table senes Bye (led araho boranes) In esses where the nomenclature 1s ambyguoe, 2 for example for pets ‘Sorane sis wus to mlade the number of open atoms the Rane “eile 110 The tw sens of trans “rscna borane Balen BiH, Goan mS 8S Bah pemowney 2 @ ly Fetarne 10 “a? 108 BNE ocuborne 12 dee Bi geterne 11 Bul heaton 12 Bal cetaerae 1 Bs foutirc or Dah Seborne Preparation Diborane 1 the simplest and mos tude ofthe hyde. I wed 1° prepare the fugher oranes, sed 5 a9 amporant reagent i syathete fxg chamstry Far th ner purpose nol generated nat I averse reaen fe the proacton of erganoboranes whe ane seal tmemacstes ye organic anthese Alwinaraly diborane wed 983 powerfolelectrophie reducing agent Tor cern fnetonsl groups Tt "Nook stes wih a hugh elecron dept such a Um yan ti its $n Ore carbonyl compounds ‘ R—CaN- RCHANH, ONO} RN; Ve ROCHO— RCH.OH Diborane may be prepared by vancty of methods Boranes were fst prepared by Allred Stock, who pronered the Branch o!, GemsBORON HYDRIDES | [391 between 1912 and 1936. He heated Mg and B to give magnesium boride MgxBo, and then treated this with orthophosphoric acid. The reaction gives a mixture of products, There were enormous difficulties with this early work because the compounds were highly reactive, flammable, and hydro- Iysed by water. Stock developed vacuum line techniques, which were pre- viously unknown, to handle these reactive compounds. This preparative method has now been superseded except for making BeHyo. Mg:B, + H;PO, — mixture of boranes““>BH, magnesium mainly ByHyo diborane onde Many other methods have been used: BO; + 3H, +2Al 750 atmospheres, 150°C. BoH, + ALO; 2BF; + 6(NaH > BH, + 6NaF ms Bs ‘There are several convenient laboratory preparations: 1. Reducing the-etherate complexes of the boron halides with Li[AIH,). 4[Et,0 - BF] + 3Li[AIH,] “28, + SLifAIF,] + 4Et,0 2, Reacting Na[BH,] and iodine in the solvent diglyme. Diglyme is a polyether CH;OCH,CH,OCHCH,OCHs. an diglyme solution 2Na[BH,] + 1p 3. Reducing BF; with Na[BH,] in diglyme. B,H, + Hp + 2Nal 4{Et,0 - BF} + 3Na[BH,] ““"* 28,4, + 3Na[BF,] + 4Et,0 Method (3) is particularly useful when diborane is required as a reaction intermediary. It is produced in situ, and used without the need to isolate or purify it, Diborane is a colourless gas, and must be handled with care as it is highly Feactive. It catches fire spontaneously in air and explodes with dioxygen. The heat of combustion is very high. In the laboratory it is handled in a vacuum frame. Since it reacts with the grease used to lubricate taps, special taps must be used. It is instantly hydrolysed by water, or aqueous alkali. At red heat the boranes decompose to boron and hydrogen. BH, + 302 > 2B,03 + 3H,0 AH = —2165kJ mo}! BH, + 6H,0 — 2H3BO; + 3H, Most syntheses of higher boranes involve heating BzH,, sometimes with drogen. A complex reaction occurs when B2H, is heated in a sealedfade Vans higher bornes ate Jormed (BAPyp Bedi, By aed Bath) ‘The BiH molecule probably breaks mio the very rescne tstermetate (BTL) wiv has only easient existence and reacts wh Ble swing another termediate (B;!s} Ths loses hydrogen forrng {Batis whch tests ith more (DH) 10 ve By Ina sila ay 3 tansy of igherboranes ase formed depending onthe ent roneitons For exmple (6h a 80-80, 200 atmospheres) Bitle+ Bie (capa 2 200-250°0) ‘alle Hy > Bl (Gow eyo 9 sealed tube 150°C) Bate» Bete Most ofthe higher branes are gus, but Bui andPHysare soles As ‘he molecular weight rerenser, the fradualyDecome moe table a, sndlesssenive fo water Byly inert a a sndcan be recovered ter sgucous salons At one tne te bores were considered as poste togh energy rocket fuse The mum was to tpl hyrocarbon foes ulay aterat an meses Over atone Of Bice wes made fr ths furposeIneest in ths ase dappeared when f was found hat combs {tonto B05 wat meomplete, Because of th the exhaust porate of (he rocket beexme paily blocked wih an inlale BO ply REACTIONS OF THE BORANES Hideobocaton ‘Avery smportant reaction oecur between BA, (ot BE, 4 NaBH) and alisnge aa aligns, Ba + 3RCH—CHR— B(CH,—CHLR), Jost + IRC=R— BIRC=CHR), ‘The renctons ate camed cum dy ether under an atmosphere of mt gen because B3Ny andthe prodoxs are very reactive The aiyborae Products Ry are no usualy wolated ‘They May be converted as follows 4 to hydceatbons ty teatzicot wah arbor as, 4 to alcohols by reacnon nh ltaline 10 of 3 tether ketones or exrboryhe nas By onan wah ebvome sa ‘The complete process us called hydroborston, and result oF anydeogenation, or ax hydeavon, Where the organi molec snot 37. ‘eval tbe eacion felons the nt Markova rie, that Bache {0 he lest subsisted Catom BR, + SCH,COOH + 3RH + B(CH,COO),393 | { REACTIONS OF THE BORANES B(CH2-CH2R)3 + H,02 > 3RCH,CH20OH + H3BO3 primary alcohol R R ‘ 0, ' a. Dh—U™Lhmrmrm—O / / R' s R’ ketone (CHs-CH,);—B “"" cH,COOH carboxyhe acid (CH3°CH,);—B + co SM (CH, -CHz)s—CBO], HS, (CH;-CH,}COH Hydroboration is a simple and useful process for two main reasons: 1. The mild conditions required for the initial hydride addition, 2. The variety of products which can be produced using different reagents to break the B—C bond. H.C. Brown won the Nobel Prize for Chemistry in 1979 for work on these organoboron compounds. Reaction with ammonia All the boranes act as Lewis acids and can accept electron pairs. Thus they react with amines, forming simple adducts. They also react with ammonia, but the products depend on the conditions: BH, + 2(Me);N —> 2[Me3N- BH3] BH, + NH; 22 ™\__, B,H,-2NH, Tow temperature ‘excess NH (BN), boron minde Igher temperature ratio 2NH, 1B:H, BaN3H, 4 Ingher temperature The compound B,Hg-2NH; is ionic, and comprises [H;N > BH) — NH]* and (BH,]~ ions. On heating, it forms borazine. Boron nitride is a white slippery solid. One B atom and one N atom together have the same number of valency electrons as two C atoms. Thus boron nitride has almost the same structure as graphite, with sheets made up of hexagonal rings of alternate B and N atoms joined together. The Sheets are stacked one on top of the other, givi Sar n top of the other, giving a layer structureTe cor DENTS _ ta tatie Ay Av 7 ' (aan rape nh nga A Gn ©) eeeatne Petes le 38S ae tee 0) en mie pai orazine ByNH is sometimes called “inorganic benzene Beaute i structure shows Some formal silty with benzene, with delocalized ‘ecirons and aromatic characte, Their phys! poperies ate ho St Bovcne ad subtedboraes row made ooh + nc pose, Meine asi, ‘Borzine forms re compleses such at B,NsHiCi(CO) with trasion etal compounds. Borie is considerably more reactive than benzee, snd adiion reasons osu quite ted BAN, +3 BNC,STRUCTURES OF THE BORANES | [395 If heated with water, borazine hydrolyses slowly. B3NiH, + 9H,0 > 3NH; + 3H3BO3 + 3H2 Some other reactions of boranes BH, + 6H,0 > 2B(OH); + 6H2 . 2H;BO, + 6H, BH, + 6MeOH > 2B(OMe); + 6H BH, + 2EtS > 2[EtS > BH] BH, + 2LiH -> 2Li[BH,] 2B,H, + 2Na— Na[BH,] + Na[B;H,] (slow) ByHe + HCl —> B,HsCl + Ho BH, + 3Cl > 2BCl; + 6HCI STRUCTURES OF THE BORANES The bonding and structures of the boranes are of great interest. They are different from all other hydrides. There are not enough valency electrons to form conventional two-electron bonds between all of the adjacent pairs NA of atoms, and so:these compounds are termed electron deficient. 8. oe In diborane there are 12 valency electrons, three from each B atom and if aod, six from the H atoms. Electron diffraction results indicate the structure shown in Figure 12.11. Figure 12.11 The structure of ‘The two bridging H atoms are in a plane perpendicular to the rest of the “borne. molecule and prevent rotation between the two B atoms. Specific heat Measurements confirm that rotation is hindered. Four of the H atoms are ina different environment from the other two. This is confirmed by Raman spectra and by the fact that diborane cannot be methylated beyond Me,B,H, without breaking the molecule into BMe3. _: The terminal B—H distances are the same as the bond lengths measured in non-electron-deficient compounds. These are assumed to be normal covalent bonds, with two electrons shared between two atoms. We can describe these bonds as two-centre two-electron bonds (2c-2e). Thus the electron deficiency must ve associated with the bridge groups. The Nature of the bonds in the hydrogen bridges is now well established. Obviously they are abnormal bonds as the two bridges involve only one electron from each boron atom and one from each hydrogen atom, making a total of four electrons. An sp° hybrid orbital from each boron atom overlaps with the ‘Is orbital- of the hydrogen. This gives a delocalized molecular orbital covering all three nuclei, containing one pair of electrons and making up one of the bridges (see Figure 12.12). This is a three- feane, two-electron bond (3c-2e). A second three-centre bond is also(THE ono s Beevens gre 1.12 uve of spproutely 5p hyd orbs fom, 8 wih an + ‘bal fem 1 gies "baone shaped! nee ert wo eton Sond. ‘The higher Boras have an open cage structure (Fite 12.13) Bath onml d multscentre Bonds are requ fo expan these structures: 1. Termanal B—H bonds, These ate noua covalent bonds, ha i to centre two-electron (202) bons, 2, BOB bond, There are aio normal 222s bons 208 nove 8 ‘es Tevsteome Bie Peston By re 12.13 Susur of some traes () Dicie Bil, wth to he See bpd had epi enh ae teste Brrr toads and one ooeg Renata sy mer eas [oes fom asqniebnedpyaniaefitortaceernte Bef Bons ‘masa bon ro heap bata foe 8s ie gene: © Fenabarnet Ballon wer the baz sons frm a noted sre ed Pid wiih ects te” Bbondrandtecese BB rio te tnpl fs. (e) Besteane (Aer A‘. May ‘pel emer ene 97)ORGANOMETALLIC COMPOUNDS 397 Three-centre bridge bonds including B. . .H. . .B asin diborane. These are 3c-2e bonds. |. Three-centre bridge bonds including B...B...B. similar to the hydrogen bridge in (3). These are called ‘open boron bridge bonds’, and are of the type 3c-2¢. . Closed 3c-2e bonds between three B atoms. as Decaborane-14 has ten B atoms. This number is two short of being able 10 form a regular icosahedron. An icosahedron has 2 corners and 20 faces. It isa closed cage structure, and is particularly stable. The two extra atoms. required to complete the cage may be added by reacting ByyHjs with an ethyne, forming a carborane (Figure 12.14). w ByHys + RC=CR > ByQHwRz Alternatively two B atoms may be added to complete the cage by reacting ByoHys with MesN > BHs. BiHyy + 2Me;N+BH, — 2{Me,NHJ]*[By2Hi2]*" ORGANOMETALLIC COMPOUNDS Besides the carboranes and the alkylboranes discussed earlier, all the Group 13 trihalides will react with Grignard reagents and organolithium reagents, forming trialkyl or triary! compounds: BF, + 3C;HsMgl > B(C3Hs)3 AIC]; + 3CH;Mgl > Al(CH3): GaCh + 3C:HsLi + Ga(C,Hs), InBrx + 3CsHsLi > In(CgHs)s The aluminium compounds are unusual because they have dimeric struc- tures, and appear to have three-centre bonds involving sp* hybrid orbitals on Al and C in Al—C—AI bridges (Figure 2.15). Another important route to organoaluminium compounds is from alu- ae metal and H>. The two clements do not react directly to give Hi. However, alumimum does take up hydrogen in the presence of aluminium alkyl catalysts (Ziegler catalysts). Al + JH) + 2EtQAl > 3Et,AlH Alkenes, may be added to Al—H bonds. EvAIH + HyC=CH, > Et,Al—CH, ethene CHy ie. EtsAl Figure 12.14 Structure of orthocarborane, one of the th tsomertc forms of the icosahed carborane ByC2HR2. (After A.G. Massey, The Typical Elements, Penguin, i972.) NN HM Now “. Figure 12.15 Structure of aluminium trimethyl dimer.Cr coor acai 4 At 90-120°C and 100 stmorpheres peste, ethene molecules are stony Ineered nt the AIC bons 7 Cis 7 Cie CH: Gilly (Cis CH, Catt MOG ie AIL GH, AIL (CH, CH), Cae Nam Van \( ap, GH Lang chains up to Cay may be grown Hydrolys of these longs ‘hmm slomnum lke gives sag chun hydrosebons called pale Slene or polythene Formed in this way these ae low molest weg Doiyers (or ahgomers). and ae of no commer use ICs transom Fetal ett such as TC (Nats east) wsed then polymenaton ‘Srouch quckerFartheqmae the easton doesnot requre 2 high pres- fre and'a much higher motel weight polymer «produced These ‘hgh molecular weight polymers ae very important 35 One route to com> ‘meron! polythene (see Chapter 20 under “Orgeoometai compounds) “Acobol math carn feng of about C,q are priced Irom ene by rowing stable alumna allyl, oxi wth strand then bye Sang wah water Reacon ofthese slohots wth SOy ges suipoates R--SOgH whch ae then neuraled w make Bodepadable deren (Chiy=(CHyOS05 Na" (Detergents ae dncessed m Group Tourer S04), "Aluminum alls catayee the derzaton of propene wth forma- on ot woprene 2H CH=cHt,"“LcHt CH, CH; C=C I oh SS cc CCH + cH cH ‘The ute of slemantum aytsm producing alcools and woprenew of considerable indus portance (Commercal polythene ss made {vo ways, ether ving amar catalysts or by a perbndesnduces re ‘adel polymerzation, rather han wth aura sys) FURTHER READING Borer Ree (967 Ror Has Ld Brown HE (91) Boron Orne Chomry Conn net res Brown, #16 191) Oem Spurs Borne Whey New Yon Broan” HC (05%) ign edarno "Aa pat loon ia sane Calan 1 etd owt A¥ (0) ox year eters Ae Grnewmenibe Chew 18 sett cot Und CF 191) A ett esaicinn of rt stuces wth ‘phantom hyinted boat Migr Chom Male? 3