Indium-based liquid clathrates. II. Inclusion compounds derived from salts of the tetrachloroindate anion,InCl 4 − , and the crystal structure of [Li·15-c-5] [In(CH3)3Cl] (15-c-5=15-crown-5)

Indium(III) chloride reacts with 12-c-4 to give the 1:1 adduct [InCl₃·12-c-4]. This complex is a convenient In precursor to liquid clathrates. [InCl₃·12-c-4] reacts with LiCl to form [Li·12-c-4] [InCl₄]. When the reaction is carried out in the presence of an aromatic solvent such as toluene, a liquid inclusion complex forms readily. It has been determined that the C₆H₅CH₃:[Li·12-c-4] [InCl₄] ratio is 2. Alkylation of the 15-c-5 adduct of InCl₃ with methyllithium yields [Li·15-c-5] [In(CH₃)₃Cl]. The salt fails to form inclusion complexes with aromatic molecules. This compound has been characterized using single crystal X-ray diffraction. The molecule belongs to the monoclinic space groupP2₁/n, witha=7.515(2),b=18.952(6), andc=13.938(7) Å, =95.12(3)° andD _calc=1.43 g cm^–3 for Z=4. Least squares refinement based upon 2348 observed reflections led to a finalR=0.039. Supplementary Data relevant to this paper have been deposited with the British Library under number SUP82054 (20 pages).     

Polymerization of phenylacetylene catalysed by RhTp(cod) and RhBp(cod) in ionic liquids: effect of alcohols and of tetraammonium halides

RhTp(cod) ( 1 ) and RhBp(cod) ( 2 ), almost inactive in CH₂Cl₂, became good catalysts of phenylacetylene polymerization in ionic liquids ([bmim]Cl, [bmim]BF₄: bmim = 1‐butyl‐3‐methylimidazolium, [mokt]BF₄: mokt = 1‐methyl‐3‐oktylimidazolium, [bumepy]BF₄: 1‐butyl‐4‐methylpyridinium) and in CH₂Cl₂ in the presence of tetraammonium halides ([R₄N]X, R = Bu, Et; X = Cl, Br). The highest yields of polyphenylacetylene with catalyst 1 were obtained in [bmim]Cl at 65°C (64% after 2 h) and in [mokt]BF₄ at 20°C (56% after 24 h). In alcohols (CH₃OH, (CH₃)₂CHOH, (CH₃)₃COH) as solvents, up to 100% of the polymer was produced. When a mixture of an ionic liquid and CH₃OH was used as the reaction medium, the polymer yield was similar to the yield achieved in an ionic liquid only, but the molecular weight increased remarkably. Tetraammonium salts, [R₄N]X, are co‐catalysts for 1 , and the yield of the polymer increased in the order [Et₄N]Br < [Bu₄N]Br < [Et₄N]Cl < [Bu₄N]Cl. Polymers with molecular weights from 6900 to 38 800 Da were obtained with catalyst 2 in [R₄N]Br or [R₄N]Cl, whereas in ionic liquids ([bmim]Cl, [bmim]BF₄) the corresponding molecular weights were higher, from 51 300 to 60 300 Da. Copyright © 2004 John Wiley & Sons, Ltd.     

Synthesis and Chloride Affinity of Sterically Demanding Ditopic Lithium Bis(pyrazol‐1‐yl)borates

The synthesis and full characterization of the sterically demanding ditopic lithium bis(pyrazol‐1‐yl)borates Li₂[p‐C₆H₄(B(Ph)pz^R₂)₂] is reported (pz^R = 3‐phenylpyrazol‐1‐yl ( 3 ^Ph), 3‐t‐butylpyrazol‐1‐yl ( 3 ^tBu)). Compound 3 ^Ph crystallizes from THF as THF‐adduct 3 ^Ph(THF)₄ which features a straight conformation with a long Li···Li distance of 12.68(1) Å. Compound 3 ^tBu was found to function as efficient and selective scavenger of chloride ions. In the presence of LiCl it forms anionic complexes [ 3 ^tBuCl]⁻ with a central Li‐Cl‐Li core (Li···Li = 3.75(1) Å).     

Influence of ionic liquids on actinides extraction by diphenyl(dibutyl)carbamoylmethylphosphine oxide in different solvents from nitric acid solution

Influence of ionic liquids (ILs) addition (1?C50 wt%) on extraction efficiency of actinides by diphenyl(dibutyl)carbamoylmethylphosphine oxide (Ph₂Bu₂) from 3 M HNO₃ has been studied. Am(III) distribution ratios in two-phase systems 0.1 M Ph₂Bu₂ in either DCE or CHCl₃?C3 M HNO₃ depending on the nature of additional ionic liquids: imidazolium-based ILs: [C₄mim][PF₆], [C₄mim][BF₄] and phosphonium-based ILs: PPF₆, PBF₄ and PCl were determined. The highest value of Am(III) extraction ratio change (1040) was found on addition of PPF₆ to Ph₂Bu₂ in CHCl₃. Extraction of Pu(IV) and U(VI) by 0.001 M Ph₂Bu₂ in the presence of [C₄mim][PF₆] in DCE, CHCl₃ or meta-nitrobenzotrifluoride (NBTF) have been investigated. The greatest enhancement of extraction efficiency was observed using CHCl₃, the least polar studied solvent. Using a mixture of conventional solvent and ionic liquid as a solvent for extractant enables one to increase distribution ratios and reduce viscosity of organic phase as compared with ionic liquid viscosity. The marked increase of Am(III), Pu(IV) and U(VI) extraction extent by Ph₂Bu₂ on addition of ionic liquids to the extent of 10 wt% permit one essentially to diminish amounts considerably more expensive carbamoylmethylphosphine oxide(the general name is CMPO) used in TRUEX process.     

Transformation of organic compounds in the presence of metal complexes: III. Transfer hydrogenation of alkylcyclohexanones. Effect of phosphine basicity on stereoselectivity

The transfer hydrogenation of 2- and 4-alkylcyclohexanones (alkyl = Me or t-Bu) was studied in alkaline i-PrOH with catalyst systems prepared in situ from [Rh(COD)Cl]₂ + phosphine (Ph₃P, Bu₃P). The stereoselectivity depends on the basicity of the phosphine and on the bulk and position of the alkyl substituent.     

Koordinativ ungesättigte Dirutheniumkomplexe: Synthese und Kristallstrukturen von [Ru2(CO)4(μ‐H)(μ‐S)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] und [Ru2(CO)4(μ‐X)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] (X = Cl,S2CH)

Coordinatively Unsaturated Diruthenium Complexes: Synthesis and X‐Ray Crystal Structures of [Ru₂(CO)₄(μ‐H)(μ‐S)(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)], [Ru₂(CO)₄(μ‐X)(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)] (X = Cl, S₂CH) [Ru₂(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 1 ) reacts in benzene with elemental sulfur to the addition product [Ru₂(CO)₄(μ‐H)(μ‐S)(μ‐P^tBu₂)(μ‐dppm)] ( 2 ) (dppm = Ph₂PCH₂PPh₂). 2 is also obtained by reaction of 1 with ethylene sulfide. The reaction of 1 with carbon disulfide yields with insertion of the CS₂ into the Ru₂(μ‐H) bridge the dithioformato complex [Ru₂(CO)₄(μ‐S₂CH)(μ‐P^tBu₂)(μ‐dppm)] ( 3 ). Furthermore, 1 reacts with [NO][BF₄] to the complex salt [Ru₂(CO)₄(μ‐NO)(μ‐H)(μ‐P^tBu₂)(μ‐dppm)][BF₄] ( 4 ), and reaction of 1 with CCl₄ or CHCl₃ affords spontaneously [Ru₂(CO)₄(μ‐Cl)(μ‐P^tBu₂)(μ‐dppm)] ( 5 ) in nearly quantitative yield. The molecular structures of 2 , 3 and 5 were confirmed by crystal structure analyses.     

A fast atom bombardment mass spectrometry study of the hexamethylphosphoramide adducts of phenyltin(IV) and phenyllead(IV) halides

The fast atom bombardment (FAB) mass spectra of a series of hexamethylphosphoramide (HMPA) adducts of phenyltin(IV) halides [Ph₃SnX · HMPA (X = Cl, Br, I); Ph₂SnX₂ · HMPA (X = Br, I); Ph₂SnX₂ · 2HMPA (X = Br, I)] and phenyllead(IV) halides [Ph₃PbX · HMPA (X = Cl, Br, I); Ph₂PbX₂ · HMPA (X = Br, I) and Ph₂PbX₂ · 2HMPA (X = Cl, Br, I)] in a glycerol/HMPA matrix have been investigated, and compared with their electron impact (EI) spectra. No parent ions are observed in either FAB or EI, but in the FAB spectra there is a much higher proportion of metal-containing ions which also have and HMPA molecule attached. This is the case even in a HMPA-free matrix such as p-nitrophenyloctyl ether (NPOE). The main difference in the FAB spectra is the preferential loss of halide compared to phenyl, the reverse of that observed in the EI spectra. The same trend is observed for the IE and FAB spectra of the uncomplexed organometallics. Diphenyltin dihalide · HMPA adducts in the glycerol/HMPA matrix form Ph₃Sn species which are absent when NPOE is used as the matrix liquid.     

Catalytic Conversion of Glucose into Levulinic Acid Using 2-Phenyl-2-Imidazoline Based Ionic Liquid Catalyst

Levulinic acid (LA) is an industrially important product that can be catalytically valorized into important value-added chemicals. In this study, hydrothermal conversion of glucose into levulinic acid was attempted using Brønsted acidic ionic liquid catalyst synthesized using 2-phenyl-2-imidazoline, and 2-phenyl-2-imidazoline-based ionic liquid catalyst used in this study was synthesized in the laboratory using different anions (NO₃, H₂PO₄, and Cl) and characterized using ¹H NMR, TGA, and FT-IR spectroscopic techniques. The activity trend of the Brønsted acidic ionic liquid catalysts synthesized in the laboratory was found in the following order: [C₄SO₃HPhim][Cl] > [C₄SO₃HPhim][NO₃] > [C₄SO₃HPhim][H₂PO₄]. A maximum 63% yield of the levulinic acid was obtained with 98% glucose conversion at 180 °C and 3 h reaction time using [C₄SO₃HPhim][Cl] ionic liquid catalyst. The effect of different reaction conditions such as reaction time, temperature, ionic liquid catalyst structures, catalyst amount, and solvents on the LA yield were investigated. Reusability of [C₄SO₃HPhim][Cl] catalyst up to four cycles was observed. This study demonstrates the potential of the 2-phenyl-2-imidazoline-based ionic liquid for the conversion of glucose into the important platform chemical levulinic acid.     

Zur Strukturchemie der Alkyl- und Arylhalogenoarsenate(III), [Me2As2Cl5]–, [RAsCl3]–, [R2As2Br6]2– (R = Me,Et, Ph) und [Ph2AsX2]– (X = Cl,Br)

Structural Chemistry of the Alkyl- and Arylhaloarsenates(III) [Me₂As₂Cl₅]^–, [RAsCl₃]^–, [R₂As₂Br₆]^2– (R = Me, Et, Ph) and [Ph₂AsX₂]^– (X = Cl, Br) The alkyl- and arylhaloarsenates(III) [Ph₄P][Me₂As₂Cl₅] ( 1 ), [Ph₄P][RAsCl₃] (R = Me, Et, Ph, 2 – 4 ), [Me₃PhN][PhAsCl₃] ( 5 ), [Ph₄P]₂[R₂As₂Br₆] (R = Me, Et, Ph, 6 – 8 ), [n-Pr₄N][Ph₂AsCl₂] ( 9 ) and [n-Bu₄N][Ph₂AsBr₂] ( 10 ) have been prepared and their structures established by X-ray diffraction. In contrast to the chloroarsenates(III) 2 – 5 , which all contain isolated ψ-trigonal bipyramidal anions [RAsCl₃]^–, the analogous bromoarsenates(III) 6 – 8 exhibit dimeric structures. Whereas the trans sited As–Cl distances in 2 and 3 are very similar a pronounced degree of asymmetry is apparent for the Cl–As–Cl three-centre bonds in 4 and 5 [2.396(1) and 2.602(1) Å in 5]. In 6 and 7 C_i symmetry related RAsBr₂ units are connected through long As…Br bonds [2.926(1) and 3.116(2) Å in 6 ]. The bromophenylarsenate(III) anion of 8 which contains two effectively undistorted ψ-trigonal bipyramids [PhAsBr₃]^– associated by weak As…Br interactions [3.117(2) Å]. In view of its very long bridging As…Cl distances the [Me₂As₂Cl₅]^– anion in 1 can, as 6 an 7 , be regarded as two MeAsCl₂ molecules weakly linked through a chloride ion.     

Reductive nitrosylation of tetraoxometallates—XI. Molybdate hydroxylamine reaction in the presence of cyanide: Synthesis of mono- and dinitrosyl cyan

The new molybdenum cyanonitrosyl complexes, R₂[Mo(NO)(CN)₅]·2H₂O (R = Ph₄P and Bu₄N) and [Mo(NO)(CN)₃(L-L)]·H₂O [L-L =     

Zur Reaktion von Trifluorhalomethanen mit Phosphanen

On the Reaction of Trifluorohalomethanes with Phosphanes The reactions of trifluorohalomethanes CF₃X (X = Cl, Br, I) with Ph₃P, Bu₃P, (Me₂N)₃P, and (Et₂N)₃P were investigated. CClF₃ does not react. In the reactions of CBrF₃ and CF₃I with Bu₃P in acetonitrile trifluorophosphonium salts, [Bu₃PCF₃]X (X = Br, I), are formed, whereas gaseous CF₃I and Bu₃P yield Bu₂PCF₃. Depending on the reaction conditions the aminophosphanes form either [(R₂N)₃PX]X (R = Me, Et; X = Br, I) and CF₃H or [(R₂N)₃PCF₃]X.     

Organometallic compounds having metal-metal bonds : XXIII. Hydrido(triphenylgermanium)tetracarbonyliron and its conjugate base

Reaction of Ph₃GeLi with [Et₄N][HFe₃(CO)₁₁] affords the new carbonylferrate salt [Et₄N][Ph₃GeFe(CO)₄] and the same reaction provides an alternative route to the known silicon and tin analogs. Protonation of [Et₄N][Ph₃GeFe(CO)₄] with HCl in ether-THF forms the air-sensitive, thermally rather unstable cis-Ph₃GeFeH(CO)₄. The latter protonates chloride ions in dichloromethane.     

Improved Synthesis of the [Ru(η6‐p‐cymene)Cl3] Anion: Facile Isolation under Mild Conditions

Reaction of [Ru(η⁶‐p‐cymene)Cl₂]₂ with two equivalents of [Ph₄P][Cl] in CH₂Cl₂ yields [Ph₄P][Ru(η⁶‐p‐cymene)Cl₃], containing a trichlororuthenate(II) anion. In solution, an equilibrium between the product and [Ru(η⁶‐p‐cymene)Cl₂]₂ is observed, which in CDCl₃ is nearly completely shifted to the dimer, whereas in CD₂Cl₂ essentially a 1:1‐mixture of the two ruthenium species is present. Crystallization from CH₂Cl₂/pentane yielded two different crystals, which were identified by X‐ray analysis as [Ph₄P][Ru(η⁶‐p‐cymene)Cl₃] and [Ph₄P][Ru(η⁶‐p‐cymene)Cl₃]·CH₂Cl₂.     

Synthesis and Crystal Structures of Mixed Halophenylbismuthates(III)

Synthesis and characterisation of mixed halophenylbismuthates(III) with a general formula Bu₄N[PhBiX₂Y] where X = Cl or Br; Y = Cl, Br or I; X ≠ Y are reported. The molecular structures of Bu₄N[PhBiCl₂Br] ( 1 ) and Bu₄N[PhBiBr₂I] ( 2 ) are determined by X‐ray crystallography. In mixed halophenylbismuthates, the anion exists as a dimer with bismuth in a distorted square pyramidal coordination. In the dimer the two phenyl groups occupy anti position to each other thereby minimising the repulsion.     

Die Tetracyanoborate M[B(CN)4], M = [Bu4N]+, Ag+, K+

The Tetracyanoborates M[B(CN)₄], M = [Bu₄N]⁺, Ag⁺, K⁺ The tetracyanoborate anion is prepared for the first time as the tetrabutylammonium salt by the reaction of [NBu₄]BX and BX₃ (X = Br, Cl) in toluene with KCN. After purification and recrystallization of the product from CHCl₃ colorless and needle size single crystals of [Bu₄N][B(CN)₄] are formed. After metathesis with AgNO₃ the silver salt and subsequently with KBr the potassium salt is prepared. The three salts are characterized by single crystal X‐ray diffraction (Ag[B(CN)₄] P 43m, a = 5.732(1) Å, V = 188.3 ų, Z = 1, R₁ = 0.75%; K[B(CN)₄] I4₁/a, a = 6.976(1), c = 14.210(3) Å, V = 691.5 ų, Z = 4, R₁ = 1.90%; [Bu₄N][B(CN)₄] Pnna, a = 17.765(3), b = 11.650(2), c = 11.454(2) Å, V = 2370.5 ų, Z = 4, R₁ = 6.09%) and by NMR‐, IR‐, Raman‐ as well by UV‐spectroscopy.     

A non‐PFT (polymerization filling technique) approach to poly(ethylene‐co‐norbornene)/MWNTs nanocomposites by in situ copolymerization with scandium half‐sandwich catalyst

The in situ synthesis of ethylene‐co‐norbornene copolymers/multi‐walled carbon nanotubes (MWNTs) nanocomposites was achieved by rare‐earth half‐sandwich scandium precursor [Sc(η⁵‐C₅Me₄SiMe₃)(η¹‐CH₂SiMe₃)₂(THF)] (1) activated by [Ph₃C][B(C₆F₅)₄], through a non‐PFT (Polymerization Filling Technique) approach. MWNTs nanocomposites with low aluminum residue were obtained with excellent yields even though small amounts of triisobutylaluminium were needed as scavenger to prevent catalyst poisoning by MWNT impurities. MWNT bundles were disaggregated and highly coated with Poly(ethylene‐co‐norbornene) [P(E‐co‐N)] as revealed by transmission electron microscopy. Interestingly, P(E‐co‐N) copolymers showed T_g over 130 °C as well as norbornene content over 50 mol %; both values were higher than those obtained by the cationic active species in 1 /[Ph₃C][B(C₆F₅)₄]. A series of copolymerization reactions by 1 /[Ph₃C][B(C₆F₅)₄]/AlⁱBu₃ without MWNTs produced copolymers with the same unexpected features. The NMR analysis revealed the presence of rac‐ENNE and rac‐ENNNE sequences. Thus, AlⁱBu₃ changed the stereoirregular alternating copolymer microstructure produced by 1 /[Ph₃C][B(C₆F₅)₄]. We conclude that AlⁱBu₃ is not only a scavenger for CNT impurities, but it reacts with the THF ligand to give coordinatively unsaturated active species. Finally, P(E‐co‐N)/MWNT masterbatches were mixed with commercial TOPAS to produce cyclic olefin copolymer nanocomposites with excellent dispersion of filler. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5709–5719, 2009     

Reaktionsprodukte von S7NH mit Nickel- und Kupfersalzen Darstellung und Struktur der Komplexe [(CH3)4N][Ni(S3N)(CN)2], [(C6H5)4As][Cu(S3N)2] und [(C6H5)4As][Cu(S3N)CI]

Metal Sulfur Nitrogen Compounds 18. Reaction Products of S₇NH with Nickel and Copper Salts. Preparation and Structures of the Complexes [Ch₃₄N][Ni(S₃N)(CN)₂], [(C₆H₅)₄As][Cu(S₃N)₂], and [(C₆H₅)₄AS][Cu(S₃N)Cl]. In the presence of MOH (M = K, [(CH₃)₄N]), S₇NH reacts with Ni(CN)₂ to yield, besides the three-nuclear complex M[(S₃NNi)₃S₂], the new mononuclear complex M[Ni(S₃N)(CN)₂]. The [(CH₃)₄N]⁺ salt is monoclinic, C2/m, a = 19.303(9), b =6.941(3), c=16.309(10) Å, β = 144.51⁰(2), Z = 4. The [Ni(S₃N)(CN)₂]- anion is planar, Ni being coordinated by one S₃N^? chelate ligand and by two CN^? ions. From the reaction of CuCI₂, S₇NH, and [Ph₄As]OH result the salts [Ph₄As][Cu(S₃N)₂] or [Ph₄As][Cu(S₃N)Cl], depending on the reaction conditions. [Ph₄As][Cu(S₃N)₂] is triclinic, P&1macr;, a = 7.073(3), b = 11.742(4), c = 16.439(6) Å α = 91.08°(3), β = 99.01°(3), γ = 91.58°(3), Z = 2. Two S₃N^? chelate ligands coordinate to Cu^I in a distorted tetrahedral arrangement. [Ph₄As][Cu(S₃N)Cl] is monoclinic, C2/c, a = 17.174(6), b = 13.650(5), c = 21.783(5) Å β = 100.45°(2), Z = 8. Cu^I is coordinated by one S₃N^? chelate ligand and one C1^?, resulting in a trigonal planar environment.     

Intramolecular Metal⋅⋅⋅π‐Arene Interactions in Neutral and Cationic Main Group Compounds

The role of intramolecular metal???π‐arene interactions has been investigated in the solid‐state structures of a series of main group compounds supported by the bulky amide ligands, [N(^tBuAr^≠)(SiR₃)]^? (^tBuAr^≠=2,6‐(CHPh₂)₂‐4‐tBuC₆H₂, R=Me, Ph). The lithium and potassium amide salts showed different patterns of solvation and demonstrated that the SiPh₃ substituent is able to be involved in stabilizing the electrophilic metal. These group 1 metal compounds served as ligand transfer reagents to access a series of bismuth(III) halides. Chloride extraction from Bi(N{^tBuAr^≠}{SiPh₃})Cl₂ using AlCl₃ afforded the 1:1 salt [Bi(N{^tBuAr^≠}{SiPh₃})Cl][AlCl₄]. This was accompanied by a significant rearrangement of the stabilizing π‐arene contacts in the solid‐state. Attempted preparation of the corresponding tetraphenylborate salt resulted in phenyl‐transfer and generation of the neutral Bi(N{^tBuAr^≠}{SiPh₃})(Ph)Cl.     

Nitroxide chemistry. Part XIX. Reaction of bistrifluoromethyl nitroxide with diphenylketene and related compounds (Ph2CHCOX,X  OH,Cl, NH2)

The following reactions have been accomplished: 2(CF₃)₂NO· + Ph₂CCO → Ph₂C[ON(CF₃)₂]CO₂N(CF₃)₂ → (on hydrolysis) Ph₂C[ON(CF₃)₂]CO₂H; 2 (CF₃)₂NO· + Ph₂CHCOX → (CF₃)₂NOH + Ph₂C[ON(CF₃)₂]COX (X  OH, Cl,NH₂).     

Kristallstrukturen von TMEDA‐Addukten und Salzen mit protonierten TMEDA‐Molekülen

Crystal Structures of TMEDA Adducts and of Salts with Protonated TMEDA Molecules The reaction of TMEDA with two equivalents of [BH₃(SMe₂)] in toluene at 20 °C gives the adduct [TMEDA(BH₃)₂] ( 1 ). A similar reaction of pyrrolidine with [BH₃(SMe₂)] in a molar ratio of 1:1 leads to the adduct [pyrrolidine(BH₃)] ( 2 ). TMEDA can be introduced into the coordination sphere of In³⁺ by the treatment of InI₃ with TMEDA in toluene to give the complex [InI(TMEDA)] ( 3 ). The salt [HTMEDA]I ( 4 ), containing a mono‐protonated TMEDA molecule, is the result of the reprotonation of [NH₄]I and TMEDA in toluene at 20 °C. The salts [H₂TMEDA]—[InCl₄(TMEDA)]₂ ( 5 ) and [H₂TMEDA][InCl₅(THF)] ( 6 ) are formed in the reaction mixtures TMEDA/toluene/InCl₃/HCl and TMEDA/toluene/THF/InCl₃/HCl, respectively, whereupon 6 was characterized more closely. Crystals of [In₅I₆(OH)(TMEDA)₄]I·2, 5toluene ( 7 ·2.5toluene) can be obtained after treatment of InI₃ with non‐dried TMEDA; 4 was identifed as by‐product. 1 — 7 ·2.5toluene were partially investigated by NMR methods and vibrational spectroscopy. In all cases a characterization by single crystal X‐ray diffraction was performed. According to this, all nitrogen atoms in 1 and 2 are coordinated by BH₃ groups leading to a distorted tetrahedral environment at the nitrogen and the boron atoms. In 3 a distorted trigonal‐bipyramidal coordination sphere at the In³⁺ is present. The apical positions are occupied by I3 and N3. Strong N‐H···N bridges, running along [001] is the feature in 4 ; the ^I—‐Ions are not involved into the system of H‐bridges. A ion triple, [H₂TMEDA][InCl₄(TMEDA)]₂, hold together by bifurcated H‐bridges is the dominating structural motif in 5 , whereas alternation bifurcated and linear H‐bridges, leading zu a zig‐zag chain along [100], is the build‐up principle of 6 . In 7 ·2.5toluene a complex In₅O₈ skeleton was formed, consisting of a virtual corner‐connected doubled heterocubane. At every heterocubane a corner, occupied by a metal ion, is missing. The coordination spheres of the In atoms of the complex cation are completed by TMEDA molecules and iodide ions.