4 Al Ga In TI By S. M. GRIMES Department of Chemistry The City University Northampton Square London EC1 V OHB In this chapter the developments in the chemistry of Al Ga In,and T1 which have appeared in the literature over the past year are reviewed. Emphasis this year will be placed largely on the developments in the inorganic rather than organometallic field. A general review of the chemistry of these elements has been published.' 1 Aluminium A study of A1 foils for electrolytic capacitors has been made using thermogravimetry along with scanning electron microscopy X-ray diffraction and surface area tech- niques.2 The heat developing at the oxide-A1 interface during anodizing in H2S04 has also been mea~ured.~ The temperature of the A1 anode is found to increase linearly with the current density.The effects of concentration and temperature of the electrolyte and the anodizing voltage on the heat developed in A1 have been examined. The allylation of aldehydes and ketones by various allylic bromides in the presence of water using metallic A1 has been shown to be successful.4 Two papers by Antoniu et al. are ~oncerned'.~ with the reduction of Cr"' to Cr"' by metallic Al in an alkaline medium. In the first paper the rate constants and activation energies for the solution of A1 and the reduction of Cr have been ~alculated.~ A mathematical model which has been developed to describe the reduction is the subject of the second paper.6 It has been reported' that the reaction of AlH3 with CaH or of NaAlH with CaC12 in thf gives Ca(A1H4),.4thf which crystallizes in a monoclinic lattice with thf molecules co-ordinated to the calcium atom.The i.r. spectrum of aluminium tris(fluorosulphate) prepared by reaction of Al(O,CCF,) and HS03F has been recorded* and indicates a polymeric structure containing bridging bidentate ' G. Davidson Coord. Chem. Rev. 1983 49 117. J. Komives S. Gal K. Tomor and G. Kovacs J. Therm. Anal. 1983 27 315. R. M.Salen and A. A. El Hosary J. Therm. Anal. 1983 26 263. J. Nokami J. Otera T. Sudo and R. Okawara Organometallics 1983 2 191. N. K. Antoniu A. M. Egorov N. N. Sevryukov and G. E. Ermolina Russ. J. Inorg. Chem. 1983,28,69. N. K. Antoniu N. N. Sevryukov G. E. Ermolina T. V. Yanchevskaya and A. G. Pogorelov Russ. J. Inorg.Chem. 1983 28 209. B. M. Bulychev V. K. Bel'skii A. V. Golubeva P. A. Storozhenko and V. B. Polyakova Russ. J. Inorg. Chem. 1983 28 639. S. Singh and R. D. Verma Polyhedron 1983 2 1209. 61 S. M. Grimes fluorosulphate groups giving hexa-co-ordination around aluminium. Co-ordination compounds of A1(S03F) with pyridine and bipyridyl have also been obtained. A radiochemical investigation of YbCl3-(A1Cl3) complexes in the gas phase using tracer 169Yb,in the temperature range from 500 K to 1000 K was reported' and the thermodynamic data of the complexes YbAlC16 YbA12C19 YbA13Cl12 and YbA1,ClIS formed in this temperature range determined. The nature of the ionic species formed when AlCl or A1(C104) is dissolved in anhydrous methanol has been investigated using 'H 27Al and n.m.r.spectroscopy." The principal species in AlCl solution is [A1Cl2(MeOH),]+ whilst solutions of Al(C104)3 contain the hexasolvate which exhibits a broad 27Al line presumed to be due to interaction between the anion and the hexasolvated cation. Addition of water to AlCl solutions alters the spectra and these changes are discussed. Mass spectrometry" has been used to study the composition of the volatile hydrolysis products of AlCl,. Thirteen ions of aluminium oxide and hydroxide chlorides have been identified and frag- mentation schemes for the ions of hydrolysed A1C13 have been proposed. Carbon monoxide absorbents composed of aluminium copper(1) chloride and various aro- matic solvents have been prepared and the dependence of their absorbing capacities on the electronic and steric properties of the aromatic solvents determined.I2 The 13C chemical shifts and 27Al line widths for various compositions of AlC1,- dialkylimidazolium chloride molten s-alts show' the effect of the presence of the anionic species AlCl and C1- up to 0.5 mole fraction of AlCl and of the anionic species AlCl and Al2Cl in the AlCl mole fraction range 0.5-0.66.Temperature-dependent 27Al n.m.r. results show chemical exchange between chloroaluminate anions in the aluminium chloride rich molten salts. As a follow-up to their study of solutions of chlorine in some alkali chloride melts the authors14 have reported analogous data in chloroaluminate melts of AlCl,-MCl (M = Na or Cs). From a solution of AgCl/AICl a polycrystalline material of formula Ag2[Al4Cll0O2] has been isolated." The structure consists of [A14Cllo02]2- ions with the Ag+ ions co-ordinated by five chlorines in a distorted trigonal-bipyramidal arrangement.The extended structure is a three-dimensional polymer. An optical determination of carboxylate ions such as citrate oxalate and lactate utilising flocculation of Al(OH) has been carried out.16 The authors have observed that as the size of the carboxylate ion increases so too does its masking effect towards A13+ which results in a decrease in the flocculation of Al(OH),. Three papers by Ohman and Sj~bergl'-'~ have appeared reporting equilibrium and structural studies on Al"' complexes. Redox hydrolysis and complexation equilibria in the G.Steidl F. Dienstbach and K. Bachmann Polyhedron 1983 2 727. lo J. W. Akitt R. H. Duncan and C. Setchell J. Chem. SOC.,Dalton Trans. 1983 2639. " L. I. Virin,V. N. Galyashin N. M. Kuz'min V.G. Lambrev 1. Yu.Popova I. Ya. Sabaev A. I. Chemyak and A. V. Shaposhnikov Russ. J. Inorg. Chem. 1983 28 782. I2 H. Hirai M. Nakamura and M. Komiyama Buff. Chern. SOC.Jpn. 1983 56 2519. l3 J. S. Wilkes J. S. Frye and G. Reynolds Inorg. Chern. 1983 22 3870. l4 0. Waernes and T. Ostvold Acta Chem. Scand. 1983 A37 293. l5 D. Jentsch P. G. Jones E. Schawrzmann and G. M. Sheldrick Acta Crystaffogr.,1983 C39 1173. l6 M. Muto and Y. Yamahachi Buff. Chem. SOC.Jpn. 1983 56 635. L. 0. Ohman S. Sjoberg and N. Ingri Acta Chem. Scand. 1983 A37 561. I* L. 0.Ohman and S. Sjoberg J.Chern. SOC. Dalton Trans. 1983 2513. l9 L. Ohman and S. Sjoberg Pol-vhedron 1983 2 1329. Al Ga In il 63 systems A13+ and 1,2-naphthoquinone-4-sulphonate,and A13+ and 1,2-dihydroxy- naphthalene-4-sulphonate-OH have been studied in 0.6-M Na(C1) medium at 25 *C." In the former system no stable complexes were found whilst in the latter complexes of the type AILo Al(0H)L- AIL:- Al(OH)L;- and AIL;- were formed. In the second paper18 complexation in the A13+-H3GOH- system (H3L = citric acid) has been studied with measurements being performed as potentiometric titrations in 0.6-M Na(C1) at 25 "C. Mononuclear and trinuclear Al"' citrates are formed uiz. [Al(HL)]+ [AIL] [A1L213- and [A13(OH)4L3]4-. Equilibrium constants including acidity constants of H3L have been obtained.Their final paper'' deals with a potentiometric study of Al"' pyrocatecholates and Al"' hydropyrocatecholates in 0.6-M Na(C1). Again all data can be explained with a main series of complexes uiz. AlL' AlL, AIL:- and two minor species Al(0H)L;- and A13(OH)3L3 being formed. Isotherms for the sorption of the ions CO',- HCO; CrOi- and A10 by AV-I7 and EDE-1OP resins in the Br-form have been studied.20 The static capacities and ion exchange constants of AV-17 and EDE-1OP resins in the Br-form for these ions indicate that EDE-1OP anion exchange resin in the Br-form is more suitable for purifying NaBr solutions. Lithium hydroxocarbonatoaluminate has been synthe- sized2' by treating lithium hydroxoaluminate with C02 when two moles of H20 are liberated per mole of absorbed C02.For the samples Li2O.2Al2O3-O. the parameters of 1C02. 10.5H20 and Li20.2A1,O3.O.9CO2.8.8H20 the monoclinic unit cells have been determined and their i.r. and thermal analysis curves recorded. To probe the environment of A1 atoms in non-crystalline solids such as A1203-Si02 gels soda glass and mullite precursors a recently developed technique based on magic-angle spinning n.m.r. (27Al-m.a.s.-n.m.r.) has been used.22 The crystal structure of Al( N03),9D20was determined23 by three-dimensional neutron diffraction data collected at 295 K. The asymmetric unit contains Al(D20)3,+ octahedra NO ions and three D20molecules which are not co-ordinated to A13+ ions. All nine water molecules in the formula unit are crystallographically indepen- dent and the 19 hydrogen bonds give O..-O distances in the range 2.650(2)-3.054(2)A.The hydrogen bonds donated by the D20 molecules that are co-ordinated to A13+ ions are shorter than the other hydrogen bonds. Karlik et aZ.24 have demonstrated the ability of 27Al n.m.r. to identify complexes generated by three chelating ligands namely citrate lactate and EDTA in aqueous solution at 10 mM aluminium concentration. pH-Stable complexes have been observed in a unique chemical shift position for each ligand. Substitution equilibria as a function of increasing pH have been observed for those complexes in which the ligand (citrate and lactate) displaces waters of hydration and hydroxides displace the ligands. The thermal transformation of anhydrous alumina obtained by the decomposition of the lactate citrate and tartrate of aluminium has been examined25 by thermal analysis (TG and DTA) i.r.and X-ray diffraction studies. It is found that under an atmosphere of air the thermal decomposition of aluminium hydroxycarboxylates to anhydrous amorphous alumina which transforms to a-alumina uia y 6- and 20 N. K. Antoniu N. N. Sevryukov and A. M. Egorov Russ. J. Inorg. Chem. 1983 28 94. 2' E. T. Devyatkina N. P. Kotsupalo N. P. Tomilov and A. S. Berger Russ,J. Inorg. Chem. 1983,28,801. 22 J. M. Thomas J. Klinowski P. A. Wright and R. Roy Angew. Chem. In?. Ed. Engl. 1983 22 614. 23 K. Hermansson Ada Crystallogr. 1983 C39 925. 24 S. J. Karlik E. Tarien G. A. Elgavish and G. L. Eichhorn Inorg.Chem. 1983 22 525. 25 T. Sato S. Ikoma and F. Ozawa J. Chem. Tech. Biotech. 1983 33A 415. S. M. Grimes r T 11111111 --II I II Ill1 I 141 1 1 1 1 1i 0 200 400 600 800 1000 0 200 400 600800 1000 Temperature ("C Figure 1 TGA and DTA curves of aluminium hydroxycarboxylutes under atmospheres of uir(a) and nitrogen (b) L lactate; C citrute; T tartrate (Reproduced by permission from J. Chem. Tech. Biotechnol. 1983 33A 415) @aluminas proceeds as follows for Al[CH,CH(OH)COO], the decompositions of skeleton and the combustion of its decomposition products; for A1[CH2C(OH)CH2(C0O),] and A12[(CH(OH)C00)2]3 dehydroxylation decompo- sition of skeleton and the combustion of its decomposition products. Figure 1 gives examples of some of the thermal traces obtained for these decompositions.A study of the kinetics of the reversible complexation of Al"' with some substituted (salicy- 1ato)penta-amminecobalt(r1I)ions has been described.26 It is reported2' that Et Bun and Bu' aluminium dichlorides undergo 1,6-addition to a conjugated bond system O=C-C=C-C=O of para-quinones. Methyl- aluminium dichloride is inactive in this addition and triethylaluminium gives low yields. The reactivities of the quinones are observed to vary with their electron affinities and the highest yields of 1,6-addition are obtained in reactions of chlorine 26 A. C. Dash Inorg. Chem. 1983 22 837. 27 Z. Florjancyk and E. Szymanska-Zachara J. Orgnnomer. Chem. 1983 259 127. Al Ga In T1 Table 1 27Al N.m.r.parameters of organoaluminium compounds Compound 8(2'~i) C.N. i-Pr,Al 256 3 i-Bu,Al 276 3 t-Bu,Al 255 3 Me,A1 153 4 Et3AI I54 4 n-Bu,Al 152 4 Et2AlH 157 4 Et2AICI 167 4 Et2AlNEt2 160 4 Et2A10Me 146 4 Et AlOEt 151 4 Et,AlO(CH&OEt 151 4 Me,AlO(CH,),OMe 121 5 Et2A10(CH2)20Me 121 5 Et,AlO(CH,)2OEt 126 5 Et2AlO(CH2)2NEt2 112 5 (acac) A1 0 6 derivatives of 1,Cbenzoquinone. The results have been discussed in terms of a radical mechanism involving a homolytic cleavage of the AI-C bond. The reaction of (C6H5)3P=CH2 with A1C13 in the mole ratio of 2 :1 3 :1 or 5 :1 is said2* to yield two new compounds viz. di-~-chloro-bis[bis(methylenetriphenylphosphorane)-aluminium]tetrachloride from 2 1 and p-chloro-bis[tris(methylenetriphenylphos-phorane)-aluminium]pentachloride from 3 :1 or 5 :1.These dimers bridged by chloride anions are thermally stable. Benn et al.29 have shown by the use of 27Al n.m.r. spectroscopy that in general a simple correlation exists between co-ordin- ation number and S(27Al) in organoaluminium compounds (Table 1). In addition the authors have confirmed the pentaco-ordination of the A1 atoms in Me2A10(CH2)20Me. The co-ordination geometry can be described as a distorted trigonal bipyramid in which two methyl groups and an oxygen atom are located in the equatorial plane. The properties of A'",Fe"' and Cr"' complexes of methylthy-mol blue semimethylthymol blue xylerol orange and semixylerol orange have been e~amined.~'In particular the influence of electron donating substituents on the stability rate of formation and the positions of the absorption bands of the tervalent metal complexonates has been determined.The reaction of an anion of diphenylphosphine oxide prepared by the action of sodium dihydrobis(2-methoxyethanolato)aluminateon the oxide with various men- thy1 or neomenthyl halides and sulphonates were studied3' to clarify the stereochemistry of the substitution. The reaction gave neomenthyl- and methyl- diphenylphosphine oxide in ratios from 1OO:O to 0 100. The unusual anion 28 Y. Yamamoto Bull. Chem. SOC.Jpn. 1983 56 1772. 29 R. Benn A. Rufinska H. Lemkuhl E. Janssen and C. Kruger Angew. Chem. Znt. Ed. Engl. 1983,22 779. 30 N. F. Kosenko Russ. J. Inorg. Chem 1983 68 71.31 M. Yamashita Y. Soeda N. Suzuki M. Yamada K. Tsunekawa T. Oshikawa and S. Inokawa Bull. Chem. SOC.Jpn. 1983 56 1871. 66 S. M. Grimes [A1706Me,6]- has been en~ountered~~ in the decomposition pathways of two (high oxygen-content) organoaluminium compounds K[Al,Me602] and Cs2[A12Me60]. Crystalline materials of triclinic K[AI7O6Me,,].C6H6 and cubic Cs[A1,O6MeI6]. 3C,H,Me have been isolated. The structures consist of open A1606 cages capped by the seventh A1 atom which is bonded to three alternate 0 atoms in the cage. The six A1 atoms are bonded to terminal Me groups each while the unique A1 is bonded to only one Me group. A new method has been developed33 for the determination of solvent donicity towards the Na ion that avoids solvent-solvent interactions.Using the system NaAlEt,-benzene-donor the response of the quadrupole relaxation to anion symmetry as a function of the donor Na' ratio is monitored by both 27Al line widths and methylene H absorptions. The crystal structure of y-A1B12 has been reinvestigated by single crystal X-ray diffractometry and the nature of the A1 distribution in the boron framework examined.34 The aluminium atoms are said to be distributed in the boron framework according to a simple rule as in the crystals of the a-AIBI2 structure type. The structure of Sr,AI, together with those of Ba,Ga and Sr,Ga has been determined.35 The three compounds are isotypic and the structure of SrBAl7 is characterized by the presence of isolated tetrahedral and triangular clusters of A1 atoms included in cages of 13 Sr atoms.Three types of precipitates are observed in TiAl alloys containing from 50 to 58 atomO/~AI.~~ Two types were found in the alloys Ti46Als4 and Ti42A158 both of which have ordered superstructures of an f.c.c. lattice. The third type of precipitates is present in the alloys Ti46A154 and Ti50A150. The proposed structure corresponds to the compound Ti2A1 and can be described as a stacking of six close-packed planes of type AB'ABA'B or AB'CBC'B in which the planes A are pure Ti planes and the planes A' pure Al planes. The interaction of BeF2 and AlF at temperatures of 400 500,600,700 and 800 "C and AlF3 concentrations of 0-75 mole% has been in~estigated.~~" Preliminary results on the equilibrium diagram of the AlF,-BeF2 system have been presented.BaA1,-type derivative structures can be classified according to the type of co-ordination polyhedron around the transition metal which can be a tetrahedron or a square ~yramid.~' The charge-density distribution in LiA1BI4 has been studied3 by X-ray diffractometry to elucidate the role of the metal atoms in stabilizing the structure. The results seem to suggest there is a charge transfer from the metals to the electron-deficient boron framework. Another paper contains a report on the charge-density distribution in crystals of CUA~O~.~~ The study showed that the deformation of the electron-density distribution can be well explained by assuming d-s hybridization with linear combination of the 3dz2and 4sorbitals for the valence 32 J.L. Atwood D. C. Hrnar R. D. Priester and R. D. Rogers Organornetallics 1983 2 985. 33 M. C. Day J. H. Medley and N. Ahmad Can. J. Chern. 1983 61 1719. 34 I. Higashi J. Solid Srare Chern. 1983 47 333. 35 M. L. Fornasini Acta Crystallogr. 1983 C39 943. 36 A. Loiseau and A. Losalmonie Acta Crystallogr. 1983 B39 580. 360 B. S. Zakharova and L. P. Reshetnikova Russ. J. Inorg. Chern. 1983 28 133. 37 E. Parthe B. Chabot H. F. Braun and N. Engel Acta Crystallogr. 1983 B39 588. 38 T. Ito and I. Higashi Acta Crystallogr. 1983 B39 239. 39 T. Ishiguro N. Ishizawa N. Mizutani M. Kato K. Tanaka and F. Marumo Acta Crystallogr. 1983 839 564. Al Ga In 77 67 electrons of the Cu+ ion. The solubility of A1 and Fe in LaNi, up to compositions of x = 1.5 and 1.2 respectively and the formation of continuous solid-solutions between LaNi and LaCuS have been confirmed4* by X-ray diffraction studies of the alloys of the LaNi,-,T systems where T is Al Cr Fe or Cu.The replacement of Ni in LaNi by Al Cr Fe or Cu is found to increase the stability of the corresponding hydride phases and reduce the absorption capacity of the intermetallic compounds. Phase formation in A1203-M203 systems (M = In V or Ti) has been considered as a function of temperature;l with the aid of space-energy concepts. In another paper42 the equilibrium diagram of the A120,-V205 system constructed using DTA and X-ray diffraction techniques has been presented. The temperature for the peritectic fusion of A1VO4 is found to depend on the partial pressure of oxygen in the synthesis of the system.Two papers by Fotiev et a143*44describe the use of thermodynamic and X-ray diffraction analyses to triangulate A1203-Si02-V205 Al,O,-K20-V205 and Al2O3-Na20-V2O5 and to tetrahedrate A1203-K20-Si02- V205 and A1203-Na20-Si02-V205 systems. Another study by Fotiev and Surat4 used the same. methods to triangulate systems in the subsolidus region containing orthovanadates FeVO, CrV04 AlV04 and metavanadates KVO and to tetrahedrate the FeV0,-CrV0,-AlV0,-KVO quaternary system. Three new pyrovanadates of general formula KMV207 (M = Fe Cr or Al) are formed. Results of investigations of two ternary systems uiz. A1203-B203-M20 (M = Li or Na) have been reported by Abdullaev et al.46747From the Li-~ystem~~ five new borates are formed ;2Li20.A1203.2B203; Li20.A1203.B203 and 3Li2O.Al2O3.2B2O3 ; Li20-A1203-2B203 Li20.2Al2O3-2B2O3 with melting points 730 785 760 850 and 775 "C respectively.Three new borates are formed in the Na-~ystem:~~ 5Na20.B20,; Na20.Al,03.B20 and Na20.A1,O3-2B2O3 with melting points of 750 1010 and 1025 "C respectively. The preparation structure and magnetic properties of isostructural La3MA1S7 and La3MFeS7 (M = Mg Mn Fe Co Ni or Zn) quaternary metal sulphides have been rep~rted.~' The structure of a new magnesium aluminium zirconium oxide Mg5+xA12,4-xZr1.7+0,25x012 with -0.4 5 x 5 0.4 has been determined.49 Five papers appearing in the literature are concerned with Al-containing zeolites and related minerals.The structure of basic sodalite a member of the zeolite family has been determined.50 The 1 1 alumino-silicate framework is completely ordered whereas both the 0 of the hydroxy-group and the water molecule are disordered about the body diagonal of the cubic cell. A structure refinement on mathiasite has been carried out.5' It is isostructural with the crich- tonite-group minerals AM2,03* and is characterized by dominant potassium in the 40 K. N. Semenenko L. A. Petrova and V. V. Burnasheva Russ. J. Inorg. Chem. 1983 28 107. 41 G. A. Korablev V. T. Ivashinnikov A. A. Fotiev V. E. Gladkov and A. S. Zubov Russ. J. Inorg. Chem. 1983 28 881. 42 S. M. Cheshnitskii A. A. Fotiev and L. L. Surat Russ. J. Inorg. Chem. 1983 28 758.43 A. A. Fotiev L. L. Surat and I. P. Kolenko Russ. J. Inorg. Chem. 1983 28 119. 44 A. A. Fotiev B. V. Slobodin L. L. Surat and T. P. Sirina Russ. J. Inorg. Chem. 1983 28 588. 45 L. L. Surat and A. A. Fotiev Russ. J. Inorg. Chem. 1983 28 1059. 46 G. K. Abdullaev P. F. Rza-Zade and Kh. S. Mamedov Russ. J. Inorg. Chem. 1983 28 428. 47 G. K. Abdullaev P. F. Rza-Zade and Kh. S. Mamedov Russ. J. Inorg. Chem. 1983 28 11 5. 48 K. S. Nanjundaswamy and J. Gopalakrishnan J. Solid State Chem. 1983 49 51. 49 P. Tassot G. Konig F. Liebau and F. Seifert J. Appl. Cryst. 1983 16 649. 50 I. Hassan and H. D. Grundy Acta Crystaflogr. 1983 C39 3. 5' B. M. Gatehouse 1. E. Grey and J. R. Smyth Acta Crystallogr. 1983 C39,421. 68 S. M. Grimes large-cation A site.Partial disorder in the M-cation sublattice is interpreted as due to the partial occupation of a second anion site by large cations. The structure of dehydrated zeolite 3A (Si/Al = 1 .O1) has been determined by neutron profile refine- ment.52 27Al N.m.r. has been showns3 to be a valuable tool in probing the co- ordination quantity and location of A1 atoms in chemically treated zeolites. Heats of adsorption of pyridine and ammonia were respectively measureds4 on Al-deficient H-Y zeolites using a microcalorimeter at 473 K. The calorimetrically determined acidity was discussed in relation to the positional difference between 3640 and 3550 cm-' OH acidic sites and compared with the catalytic activity. The reaction of LiA1H4 with C02 or NaHCO at elevated temperatures has been inve~tigated.~~ From their study the authors concluded that methane and ethene the primary products of each reaction are probably the explosive reaction products formed when C02 fire extinguishers are used on LiAlH4 fires.The catalytic cracking of slack wax with molten mixtures of A1C13 and AlBr3 as catalyst was investigateds6 in an atmospheric semi-batch reactor at low temperatures of 100-160 "C. The effect of parameters such as reaction temperature HCl catalyst composition and concentra- tion on the cracking rate and product distribution has also been investigated. Two papers report the use of AlP04 catalysts. One deals with the application for the first time of the Hammett equation in the esterification of substituted benzoic acids (m-MeO p-MeO m-Me p-Me H m-NO, m-C1 and m-Br) catalysed by AlP04 of the F type.57 The other reportss8 an investigation of the skeletal isomerization of cyclohexene in a microcatalytic pulse-reactor using several A1 orthophosphates (Al/P = 1) as catalysts.The kinetics of leaching of Raney Ni-A1 alloy (Ni 50% w/w) with alkali has been studied59 in an agitated reactor by measuring the rate of H2 evolved in the leaching process at constant alkali concentrations. The effects of process parameters such as temperature type and concentration of alkali particle size of the alloy and stirring speed on the leaching process have also been investigated. Finally a method for the interpretation of the Warren-Averbach mean-squared strains and its applica- tion to recovery in aluminium has been presented.,' 2 Gallium The isolation and crystal structure of [(c,H~)~G~.G~C~,],.~C,H, has been reported6' and is the first structurally characterized benzene complex of a univalent main-group metal.It consists of cyclic centrosymmetrical [(C~H,),G~'G~''~CI,]~ units and iso- lated benzene molecules. 52 J. M. Adarns and D. A. Haselden J. Solid State Chem. 1983 47 123. 53 J. Klinowski J. M. Thomas C. A. Fyfe G. C. Gobbi and J. S. Hartrnan Inorg. Chem. 1983 22 63. 54 Y. Mitani K. Tsutsurni and H. Takahashi Bull. Chem. Soc. Jpn. 1983 56 1921. 55 B. T. Thompson T. N. Gallaher and T. C. De Vere Polyhedron 1983 2 619. 56 Y. Ohtsuka K. Oizurni and Y. Tamai Bull. Chem. Soc. Jpn. 1983 56 2716.57 J. V. Sinisterra J. M. Marinas and A. Llobera Can. J. Chem. 1983 61 230. 58 J. M. Carnpelo A. Garcia J. M. Gutierrez D. Luna and J. M. Marinas Can. J. Chem. 1983 61 2567. 59 V. R. Choudhary and S. K. Chaudhari J. Chem. Tech. Biotech. 1983 33A 339. 60 M. J. Turunen Th.De Keuser R. Delhez and N. M. Van der Pers J. Appl. Crystallogr. 1983 16 176. 6' H. Schrnidbaur U. Thewalt and T. Zafiropoulos Organomerallics 1983 2 1550. 62 P. G. Nelson and R. V. Pearse J. Chem. Soc. Dalton Trans. 1983 1977. 63 R. W. Berg and N. J. Bjerrurn Polyhedron 1983 2 179. Al Ga In TI 69 The standard enthalpies of formation at 25 "C have been determined by solution calorimetry6 for a number of potassium hexafluorometallates(Ir1) of the elements from Sc to Ga.The value obtained for K,GaF6 was -300 1 kJ mol-'. The reaction between sulphur and gallium in chlorobasic melts at ca. 500 "C has been studied6 by visual observation and Raman spectroscopy. The results suggest the formation of charged long chains (-GaCl,-S-GaC1,-S-) in these melts and the presence of the radical anion S under certain conditions. Absorption spectroscopy has been to study the formation of gaseous complexes between NdC1 and GaC1 in the temperature range 600-1000 K and at total pressures ranging from 5 to 20 atm. Thermodynamic model calculations indicate a stepwise build-up of the gas com- plexes with the formation of the molecules NdGaCI, NdGa2C19 NdGa3Cl12 and NdGaCl,,. The thermal expansion tensor of P-Ga,03 was determined65 from low-temperature X-ray diffraction.At T = 250 K the principal directions of the tensor are close to the mean directions associated with the various chemical bonds of the monoclinic structure. Alkali metal gallates have been synthesized and their homogeneity confir- med by X-ray diffraction.66 The thermal properties of the compounds Ga203 LiGaO, NaGa02 KGa02 RbGaO, and CsGaO, have been investigated by differ- ential thermogravimetry. All gallates melt congruently except the Cs derivative which melts incongruently. Another paper reports6' on the relationship of crystallographic polarity to piezoelectric pyroelectric and chemical etching effects in Li2Ge03 and LiGaO single crystals. The crystal structure of GaLa30S28 has been determined. The La atoms are in eight- and nine-fold co-ordinations and the Ga atom has a tetrahedral environment.The structure contains rings of 0-La-0-La which form chains parallel to the b direction. Ghemard et a169have identified Ga2Se to be a superstructure of the basic distorted sphalerite-type. Ordering of metal vacancies involves two different Se-atoms surrounding infinite chains of vacancies running in the b-direction and the particular stacking sequence abca'b'c' derived from ABC close packing for Ga atoms. The reactions of (C6H5),P=CH2 with GaC1 in a 2 1 3 1 or 5 1 mole ratio yield2* two new compounds viz. di-p-chloro-bis[bis(methylenetriphenylphos-phorane)gallium]tetrachloride from the 2 :1 ratio and p-chloro-bis[tris(methyl-enetriphenylphosphorane)gallium]pentachloride from the 3 1 or 5 1 ratio.Elec- trolysis of dimethylmagnesium in thf with a gallium anode is reported7' to yield the adduct GaMe,-thf directly. The trialkylamine and trialkylphosphine adducts GaMe3-L (L = NEt, PMe, or PEt,) are obtained by direct addition of an excess of L to GaMe,.thf. Free GaMe is obtained by reaction of Me1 with a Mg-Ga alloy in an ether solvent. The nature of the reactions that occur between Ga(CH,SiMe,) and In(CH,SiMe,) with alkali metal hydrides has been reinvesti- 64 T. Foosnaes and H. A. Oye Inorg. Chem. 1983 22 3873. 65 D. Dahy and J. R. Gavarri J. Solid Slate Chem. 1983 49 107. 66 A. A. Zakharov and I. S. Shaplygin Russ. J. Znorg. Chem. 1983 28 59. 67 A. S. Bhalla L. L. Tongson and R. E. Newnham J. Appl.Crystallogr. 1983 16,138. 68 S. Jaulmes A. Mazurier and M. Guittard AC~Q Crystallogr. 1983 C39 1594. 69 G. Ghemard S. Jaulmes J. Etienne and J. Flahaut Acta Crystallogr. 1983 C39,968. 7o A. C. Jones D. J. Cole-Hamilton A. K. Holliday and M. M. Ahmad J. Chem. Soc. Dalton Trans. 1983 1047. S. M. Grimes Figure 2 The arrangement of gadolinium-oxygen dodecehedra gallium-oxygen octahedra and gallium-oxygen tetrahedra in Gd,Ga,O garnet (Reproduced by permission from Acta Chem. Scand. 1983 A37 203) gated.71 Contrary to previous reports KGa(CH2SiMe3)3H and KIn(CH,SiMe,),H were isolated and their crystal structures determined. The gallium hydride derivative is thermally stable under the normal synthetic conditions and does not convert into KGa(CH2SiMe3) and SiMe as originally proposed.Extraction of Ga"' with decanoic acid in several solvents was carried at 25 "C and at an aqueous ionic strength of 0.1 mol dm- (NaClO,). The organic solvents used were toluene chlorobenzene 1,2-dichloroethane and octan- 1-01. It was found that the less polar the solvent the more extensive was the polymerization of the extracted decanoates. The formation of Ga lanthanide and vanadium complexes with catechol violet and cetylpyridinium bromide has been in~estigated~~ spectrophotometrically. The influence of the complex-forming ion on the principal physiochemical characteristics of the complexes has been examined. The component ratio in the complexes has been found the mechanism of the reaction established and the stability constants of the complexes calculated.Belin and Ling74 have surveyed the preparation and structural properties of the intermetallic phases of gallium and alkali melts. Unlike the already known phases of Ga with Li or Na the structures of the recently discovered phases Li3GaI4 Na,,Ga,, KGa, K3Ga13 RbGa, RbGa, and CsGa are characterized by stackings of co-ordinated gallium polyhedra such as icosahedra octadecahedra dodecahedra and undecahedra. In these phases the alkali metals stabilize the gallium framework by giving their valence electrons. The structures are interpreted according to Wade's electron counting procedure. The two compounds Ba8Ga7 and Sr8Ga7 are isotypic with Sr8A1735 and their structures are characterized by the presence of isolated tetrahedral and triangular clusters of Ga atoms in cages of 16 alkaline earth atoms.The structural parameters for Gd3Ga5012 garnets (Figure 2) have been refined with single crystal diff ractometer data.75 High quality crystals were obtained when 7' R. B. Hallock 0.T. Beachley Y.-J. Li W. M. Sanders M. R. Churchill W. E. Hunter and J. L. Atwood Inorg. Chem. 1983 22 3683. 72 H. Yamada S. Imai and E. Takeuchi Bull. Chem. SOC.Jpn. 1983 56 1401. 73 L. I. Ganago L. A. Alinovskaya L. N. Bukhteev and N. N. Ishchenko Rum. J. Znorg. Chen 1983 28 52. 74 C. Belin and R. G. Ling J. Solid State Chem. 1983 48 40 75 J. Sasvari and P. E. Werner Acta Chem. Scand. 1983 A37 203. Al Ga In TI 71 prepared in the presence of small amounts of CaO.From the diffraction data however no significant differences between calcium and non-calcium induced crys- tals were detectable. The structure76 of Ga,Sn2S is essentially built up from two kinds of sheets parallel to the (100) plane alternately a sheet of [GaS,] tetrahedra and a sheet of [Sn2Sll],,. The [Gas,] tetrahedra are linked in groups of two with their opposite edges shared. The equilibrium diagrams of the Ga2S3-PbS and Ga2S3Pb sections have been con~tructed'~ by physiochemical methods. The Ga2S3- PbS section is quasibinary. The ternary compound PbGazS4 which has a homogeneity region of 1.5 mole% is formed at the 1 1 molecular ratio of the components. Another paper by Rustamov ef reports that the magnetic properties of solidified melts of the FeSe-Ga2Se3 system have been studied.All the intermediate solidified melts are paramagnetic in the temperature range 80-300 K and the temperature depen- dence of the magnetic susceptibility obeys the Curie-Weiss law. The structures of Pb3GeGa10020 and Ba3SnFe,,02 have been determined79 and are found to be isostructural with each other and with Pb3GeAl,0020 and Ba3TiAl10020. The structure consists of a framework of six-membered rings of tetrahedra which form a ribbed plane. These planes are connected by a string of octahedra and by an M2+ ion in octahedral co-ordination. The other M2+ ion is situated inside the rib of the ribbed plane and has irregular seven or eight co- ordination. Finally it is reported" that a series of solid solutions in the system (GaxInl-x)2(SexTel-x)3,1 2 x 5 0 have been prepared by direct synthesis from a-Ga2Se3 and a-In,Te3.The samples were examined at room temperature by X-ray diffraction. In the whole range of concentrations cubic phases of defect zinc-blende types are present. 3 Indium An X-ray study of a mixed indium chalcogenide In-,,,,X3 (X = S Se or Te) has been carried out.' The semiconductor crystallizes in trigonal space group at room temperature. The unit cell content was found to be 1n'1n"'(0ct)~1n"'(tetr),~X~5 with an apparent chalcogen ratio Se :Te of 2.22 3 (S :Se :Te = 1 :2 3 from electron microprobe analysis). The chalcogen octahedron around one type of In"' atom shares edges with six distorted In"'-X tetrahedra. The possible exchange of some In"' for In' in various indium chalcogenide compounds has been discussed.The influence of added C1- and In"' on the thermal kinetics of the reaction of InCl(so1id) with aqueous nitrate solutions has been studied.82 Direct experimental proof of the activation by the C1-ion of the heterogeneous disproportionation of InCl in these solutions has been obtained and the influence of the Ino nuclei in the InCl matrix on the kinetics of the reaction demonstrated. 76 A. Mazurier F. Thevet and S. Jaulmes Acta Crystallogr. 1983 C39 814. 77 Z. D. Melikova and P. G. Rustamov Russ.J Znorg. Chem. 1983 28 919. 78 P. G. Rustamov N. Kh. Ali-Zade P. K. Babaeva M. R. Allazov Ya. N. Sharifov and D. M. Ragimova Russ. J. Znorg. Chem. 1983 28 453. 79 M. C. Cadee G.C. Verschoor and D. J. W. Ijolo Actu Crystallogr. 1983 C39 921. 80 B. Grzeta-Plenkovic S. Popovic B. Celustka Z. Ruzic-Toros B. Sentic and D. Soldo J. Appl. Crystallogr. 1983 16 415. C. Svenson and J. Albertsson J. Solid State Chem. 1983 46,46. 82 V. A. Smirnov Russ. J. Znorg. Chem. 1983 28 772. 72 S. M. Grimes Rapid diffusion of l80 ions in indium oxide during reduction-oxidation reactions has been useds3 to explain the observation that reduced-indium oxide is one of the most efficient compounds among the reduced metal oxides for reduction of H20 CO, or NO. In their paper,66 Zakharov and Shaplygin also report the synthesis of some alkali metal indates and their homogeneity has been confirmed by X-ray diffraction. The thermal properties of Inz03 LiInO, and NaIn02 have been investi- gated by differential thermogravimetry.Bulc et uZ.84985 report the structures of three oxalate complexes of indium. The In atom of the complex [In2(C204)3(H20)4].2H2084 is co-ordinated by 0 atoms in the form of a pentagonal bipyramid. These polyhedra are linked through the oxalate groups as bridging ligands thus forming infinite chains along the (001) direction. The average In-0 bond distance is 2.234(16)A to oxalate 0 atoms and 2.157(2) A to water molecules. There are three independent water molecules in the structure. The dihydrated ammonium and sodium bis(oxalato)indates(~rr)are isomorphous.8s In NH4[In(C204),]2H20 which was refined to an R value of 0.024 the In atom is co-ordinated by eight 0 atoms from four oxalate groups as bridging ligands forming a distorted Archimedean antiprism ; four In-0 distances are 2.197(4) 8 and four are 2.351(5) A.Ammonium ions and water molecules occupy the cavities between the anions and are linked to the anions and to each other by H bonds. The crystal structure of indium(r1r) dithizonate has also been determineds6 by X-ray diffraction methods at 295 K. The asymmetric unit of the structure is the mononuclear [In(Hdz),] molecule the indium atom is five-co- ordinated as a trigonal bipyramid one ligand being unidentate and co-ordinated equatorially through the sulphur [In-S 2.468(3) A] while the other two are bidentate (N S) spanning axial and equatorial positions. The axial In-N distances are 2.372(6) and 2.334(6) 8 while the associated equatorial In-S distances are 2.477(3) and 2.467(3) A.Isolation of KIn(CH2SiMe3),H from a reaction of In(CH,SiMe,) with alkali metal hydrides has been rep~rted.~ Like KGa(CH2SiMe3)3H the indium derivative crystallizes in the monoclinic space group but unlike the Ga derivative KIn(CH2SiMe3)3H decomposes at room temperature The differences in thermal stability between the two materials is related to the ease of the dissociative reactions of the four-co-ordinate anions and their relative metal-carbon bond strengths. Reductive elimination does not appear to be an important reaction path for these organo Group 3 derivatives. The reaction of (C6H5),P=CH2 with InCI3 in the mole ratio 2 1 yields28 a new compound of di-p -chloro-bis[bis(methylenetriphenylphos-phorane)indium]tetrachloride.Phase equilibria in the BaO-1n2O3 system have been investigatedx7 over a wide temperature range (1200-1600 K) and concentration (10% Ba0-60% BaO). The compounds Ba,In,Os Ba,In206 Ba21n20S cu-Ba41n60,, a-Ba4In,Ol3 and BaIn204 are formed. The lattice parameters of all these compounds were determined and their i.r. and Raman spectra studied. The theoretical vibrational spectra of the double 83 R. Otsuka T. Yasui and A. Morikawa Bull. Chem. SOC.Jpn. 1983 56 2161. 84 N. Bulc and L. Golic Acta Crystallogr. 1983 C39 174. N. Bulc L. Golic and J. Siftar Acra Crystallogr. 1983 C39 176. 86 J. McB. Harrowfield C. Pakowatchai and A. H. White J. Chem. Soc. Dalton Trans. 1983 1109. 87 T. A. Kalinina L.N. Lykova L. M. Kovba M. G. Mel’mikova and N. V. Porotnikov Russ. J. Inorg. Chem. 1983 28 259. Al Ga In TI 73 oxides LaIn03 and YSc03 with orthorhombic perovskite-type structures have been calculateds8 by the valence force-field method using the polymeric chains approxima- tion. The variation of the force constants of the La-0 bonds in LaIn03 with the In-0 distance is given. A crystal structure determination of In~Kss has showns9 that the In atoms are in four- or six-fold co-ordination and the potassium atom is in six-fold prismatic co-ordination. Far infrared reflection spectra of hot-pressed samples of the spinels MCr2S4 (M = Mn Fe Co Zn Cd or Hg) MCr2Se4 (M = Zn Cd or Hg),and MIn2S (M = Mn Fe Co Ni Cd or Hg) have been recorded” in the range from 40 to 700cm-I.From the spectra transverse and longitudinal optical phonon frequencies optical and dielectric constants and effective charges of the compounds have been calculated. A study of the interaction between In Sb and Tl has shown” that the InSb-TI section is quasibinary and triangulating in the InSb-T1 system. The crystallization regions of InSb and of T1 and the melting point (523 K) and composition of the eutectic (88 atom%Tl) were determined. The L~I~(MoO,)~-MI~(MOO,) (M = K or Rb) quasibinary sections of the Li20-M20-In20,-Mo03 quaternary systems (M = K or Rb) have been investi- gated92 to find whether ternary molybdates containing two different alkali cations and the cation of a tervalent element could be formed but no distinct ternary phases were isolated.The crystal structure of Pb,,61n8Bi4S19 has been determined.93 The structure consists of distorted In-S octahedra and mono- and bi-capped triangular prisms of Bi-S as well as bicapped triangular prisms of Pb-S all forming chains along y. The phase diagrams of the quaternary systems MS-Cr2S3-In2S3 (M = Co Cd or Hg) were by high-temperature X-ray diffraction patterns DTA and TG measurements and far-infrared spectra. Complete series of mixed crystals are formed among the spinel-type compounds MCr2S4 MIn2S4 (M = Cd or Hg) and In&. In the sections CoCr2S,-CoIn2S and CoCr2S4-In2S3 relatively large miscibil- ity gaps exist due to the change from the normal to inverse spinel structure. A series of samples in the system CuGaxIn,-,Te2 0 d x G 1 has been synthesized and characterized by X-ray diff ra~tion.~’ All the samples have a chalcopyrite-type struc- ture the unit cell parameters a and c and the ratio c/a changing linearly with x.The series (GaxIn,-x)2(SexTel-x)3 1 x z= 0 has also been examined by X-ray diffraction.80 In the In2Te3-rich region the diffraction pattern is similar to that of the disordered phase of In2Te3. 4 Thallium The solubilities of Tl’ halides and their crystallization from aqueous solutions have been studied and the corresponding crystallization induction periods have been calculated as a function of super~aturation.~~ The results were used to develop 88 N. V. Porotnikov 0.I. Kondratov and K. I. Petrov Russ. J. Znorg. Chem. 1983 28 105. 89 D.Carre and M. P. Pardo Acta Crystallogr. 1983 C39 822. 9o H. D. Lutz G. Waschenbach G. Kliche and H. Haeusler J. Solid State Chem. 1983,48 196. ” 0. V. Sorokina S. B. Evgen’ev and I. V. Mashchenko Russ. J. Inorg. Chem 1983 28 916. 92 N. N. Smirnyagina N. M. Kozhevnikova F. P. Alekseev and M. V. Mokhosoev Russ. J. Inorg. Chem. 1983 28 892. 93 V. Kramer Acta Crystallogr. 1983 C39 1328. 94 H. D. Lutz W. W. Bertram B. Oft and H. Haeusler J. Solid State Chern. 1983 46 56. 95 B. Grzeta-Plenkovic and B. Stank J. Appl. Crystallogr. 1983 16 576. 96 F. N. Kozlov G. A. Kitaev and L. V. Zhukova Russ. J. Inorg. Chem. 1983 28 268. 74 S. M. Grimes effective methods of purifying raw materials by growth of single crystals using the Stockbarger method.The thermodynamic^^^ of dissolving TI' iodide in water and 0.5 1.0 3.0 and 4.0 M aqueous solutions of sodium perchlorate and iodide at temperatures of 278 298 and 318 K have been studied by solubility and poten- tiometric methods using a Tl(Hg) electrode. Forty-five new Tl' carboxylates have been ~ynthesized~~ and characterized by their i.r. spectra and melting points. The i.r. spectra and laser Raman spectra of crystalline Tl' formate acetate propionate and acrylate have been recorded99 and the observed vibrational wavenumbers assigned to groups of atoms. In the carboxylates studied the bond between TI' and the carboxylate group is ionic in character. Two methods (the Harowitz-Metzger and the Dharwadkar-Karkhanavala) for calibrating the apparent activation energies of different T1' oxalates have been compared.loo The activation energies from the latter equation for separate samples of T1' oxalate are consistent and the activation energy for T12C204-+T120 is -109 kJ mole-'. However results from the Harowitz-Metzger method for the decomposition of different samples of TI' oxalate obtained from different sources showed considerable variation. The mixed-ligand complex formation of o-mercaptobenzoic acid and citric acid with Cd" Pb" and Tl' in aqueous KNO solutions containing Triton X-100has been investigated'" by polarography. It was shown that only one mixed ligand MA,X is formed where i is two for Cd" and one for Tl' j is one for all complexes and A and X are the o-mercaptobenzoate and citrate ligands respectively.The structure of Tl[B304(OH)2]0.5H20 has been determinedIo2 and is shown to contain a [B304(OH)2]- unit formed by one tetrahedron and two triangles. These units are linked together to form an infinite [B304(OH)2]:- chain and between these chains linked by hydrogen bonds T1+ and H20 are localized. Another borate structure of T14[B8012(0H)4]H20 has been shown'03 to contain a unit [B8012(0H)4]4- formed by four B04 tetrahedra and four B03 triangles. The units [B7010(OH)3-OBO(OH)]4-are linked together to form an infinite chain. T1' and H20 are located between the chains. Both crystal structures of Tl~"TeOI2 and TliTeO have been determined.lo4 In both compounds the Te atom is octahedrally co- ordinated to oxygen atoms with Te-0 distances of 1.936 A for the former and 1.946 8 for the latter.In the former structure the T1"' is surrounded by seven oxygen atoms sitting at the summits of a distorted monocapped trigonal prism whilst in the latter T1' is linked to three oxygen atoms forming a distorted T103 pyramid. The crystal stuctures of three other T1' materials have been reported. In the basic thallium sulphate T12TIOH(S04)2 the TI+ ions ensure bonding between [TI"'OH(S04)2] sheets.'" The structure Tl2S7N8 consists of TI+ cations and (S3N3)-and (S,N,)-anions.Io6 Rey et al. have determinedIo7 the structure of TlSbS2 which 97 I. D. Isaev V. A. Fedorov V. P. Antonova and V. E. Mironov Russ. J. Inorg. Chern. 1983 28 751. 98 T. V. Lysyak S. L. Rusakov I. S. Kolomnikov Yu. Ya. Kharitonov Russ.J. Inorg. Chern. 1983,28,756. 99 Yu. Ya. Kharitonov I. I. Oleinik and N. A. Knyazova Russ. J. Inorg. Chem. 1983 28 477. I00 S. R. Sagi K. V. Ramana and M. S. Prasada Rao Russ. J. Inorg. Chern. 1983 27 155. 101 K. C. Gupta and K. K. Sharma Bull. Chern. SOC.Jpn. 1983 56 1867. I02 M. Touboul C. Bois and D. Mangin Acta Crystallogr. 1983 C39 685. I03 M. Touboul C. Bois and D. Amoussou J. Solid State Chern. 1983 48 412. I04 B. Frit G. Roult and J. Galy J. Solid State Chern. 1983 48 246. lo' F. Abraham G. Nowogrocki B. Jolibois and G. Laplace J. Solid State Chern. 1983 47 1. 106 H. Marton and J. Weiss Acta Crystallogr, 1983 C39 959. lo' N. Rey J. C. Jumas J. Olivier-Fourcade and E. Philippot Acta Crystallogr. 1983 C39 971. Al Ga In T1 75 is built up from sheets parallel to the 010 plane formed by SbS4 moieties which are linked together.The sheets are linked by weak Tl-.S (3.50-3.66A) Tl--Sb (3.60-3.73 A) and Tl...Tl (3.62 A) interactions. Bastow et ~1.'"~ report preliminary investigations on the pyridinium ennea-chlorodithallate(II1) complex. An X-ray structural investigation on the salt is in progress. Three papers have appeared reporting the crystal structure determinations on three thallium(rI1)-containing complexes. Following a comment on their pre- viously published results on the structure of [N(C4H9),][TlI4] Glaser et uZ."~ have re-refined the structure in the space group P2,/n and have achieved better results. Jeffs et al. have determined the structures of both [TlBr3(C,H,02)]''o and T1(C4Hs02)'TlBr~.1'1The structure of the former consists of distorted planar TlBr units bridged by dioxane chairs to form chains parallel to the c-axis.The geometry around the five-co-ordinate Tl is trigonal bipyramidal. The latter contains tetrahedral TlBr ions and chains of Tl+ions bridged by l,&dioxane molecules; the geometry around eight-co-ordinate Tl+is a distorted dodecahedron. The complex [TlR,(diox)] (diox = 1,4-dioxan) has been prepared"' by the reaction of TIC13 with LiR (R = 2,4,6-C6F3H2) or of [NBu4][T1&] with HBF (R = C6F5) and subsequent addition of dioxan. The displacement of dioxan by (a) neutral ligands leads to [TlR,L] (L = OPPh3 py PPh3 or Ph2PCH2PPh2); (b) anionic ligands affords Q[TlR,X] (Q = [NBu4]+ [N(PPh,),]+; X = C1- CN- NO, or CF3C0,); and (c) metal carbonylate gives Q[TIR3M*] (M* = [Mo(cp)(CO),]-(cp = 7-C,H5) [W(cp) (CO)3I- [CO(CO)4I- Or [Mn(C0)5I-).The crystal structures of complexes formed by dimethylthallium picrate with two isomers of dicyclohexano-18-crown-6have that in both there are [Me'Tl crown]+ cations consisting of linear Me2Tl entities normal to the plane through the six 0 atoms of the ligand and the T1 atom. Figure 3 shows the environment of the cation as found in each of the picrate isomers. The interaction of the components of the Se-Tl system in the concentration range 33.33-100atomY0 Se has been studied'I4 by DTA X-ray diffraction and micro- structural analyses. The formation of the compounds T12Se and TlSe with melting points of 388 "C and 340 "C respectively was confirmed.The solubility and composition of the solid phases in the Pb12-TlI-H20 system at 25 "Chave been investigated' Is isothermally. The double compounds 3TlI.Pb12 TlIePbI, and TlI-2Pb12 have been formed. New glass formation regions have been found in the TI-B-S(Se) and TI-Ge-S ternary systems close to the Tl-S(Se) side of the concentration triangle.l16 Small additions of B and Ge raise the glass formation temperature (Tg) in comparison with the glasses of TI-S(Se) systems. From the construction of equilibrium diagrams of GeSe2-T12Se GeSe-TlSe and GeSe,-TlSe I08 T. J. Bastow B. D. James and M. B. Millikan 1.Sofid State Chem. 1983 49 388. 109 J. Glaser P. L. Goggin M. Sandstrom and V. Lutsko Acra Chem Scand.1983 A37 437. I I0 S. E.Jeffs R. W. H. Small and I. J. Worrall Acta Crystallogr. 1983 C39 1628. Ill S. E.Jeffs R. W. H. Small and I. J. Worrall Acta Crystallogr. 1983 C39 1205. 112 R. Uson A. Laguna J. Antonio Abad and E. de Jesus J. Chem. SOC.,Dalton Trans. 1983 1127. 113 D. L. Hughes and M. R. Truter Acta Crystallogr. 1983 B39 329. 114 E. Yu. Turkhima and G. M. Orlova Russ. J. Inorg. Chem. 1983 28 764. I I5 R. M. Shklovskaya S. M. Arkhipov V. A. Kuzina and T. E. Volovkina Russ.J. Inorg. Chem. 1983,28 1058. I I6 S. A. Dembovskii M. N. Brekhovskikh E. K. Voitenkova and L. M. Klimashevskii Russ. J. Znorg. Chem. 1983 28 1068. S. M. Grimes Figure 3 (a) The [Me,Tl(cis-cisoid-cis-dicycZo~exano-18-crown-6 isomer A)]+ cation and (b) the [Me,Tl(cis-transoid-cis-dicyclohexano-18-crown-6 isomer S)]' cation asfound in the crystal structure of the picrate (Reproduced by permission from Acta Crystallogr.1983 B39 329) the following intermediates were formed Tl2Ge,Se5 T12GeSe3 Tl,GeSe, T12GeSe4 and TlGeSe,. Channel structures based on octahedral frameworks have been described,"' the crystal structures of TlTi,Se8 TlVsSe8 and TlCrSSe8 deter- mined and their relationship to Tlv5s8 TlCr,S5 hollandite and psilomelane lattices discussed. Two papers repo~-t"~*'~~ the investigation by DTA and X-ray diffraction methods of the thallium chalcogenide and mercury chalcogenide systems. The interaction between In Sb and Tl has also been investigated." The double molybdates and tungstates M+Bi(EO,) (where M = Ag or TI and E = Mo or W) have been synthesizedI2' by solid-phase reactions from the component oxides and their unit cell parameters have been determined.Finally the GeSe2- TlSbSe system has been synthesized by physicochemical methods.I2* It has a simple eutectic point at GeSe2(50 mole O/0)(210 * 5 "C). The GeSe2-TlSbSe system has a glass formation region at 40-70 mole YO GeSe,. I17 M. B. Babanly and N. A. Kulieva Russ. J. Inorg. Chem. 1983 28 877. 118 K. Klepp and H. Boller J. Solid State Chem. 1983 48 388. 119 M. M. Asadov Russ.J. Inorg. Chem. 1983,28 1025. M. M. Asadov Russ. J. Inorg. Chem. 1983 28 303. 121 P. V. Klevtsov A. P. Perepelitsa and R. F. Klevtsova Russ. J. Inorg. Chem. 1983 28 363. 122 Z.G. Makoskaya and E. G. Zhukov Russ. J. Inorg. Chem. 1983 28,612.