Reaction Of InCl3 Research Articles

Structural studies and physicochemical properties of indium(III) complexes with 2-formyl-8-hydroxyquinoline-derived hydrazones

The reaction of InCl3 with 2-formyl-8-hydroxyquinoline-4-nitroimidazole hydrazone (H2L1) in ethanol gave [In(H2L1)(HL1)Cl2], complex (1), as the product. Experimental data and theoretical DFT calculations suggested that complex (1) presents coordination number (CN) 8, with one neutral and one anionic ligand coordinated to the metal center through the O-Npy-N tridentate chelating system together with two chloride ions. The reaction with 2-formyl-8-hydroxyquinoline-4-nitrobenzene hydrazone (H2L2) in methanol gave [In(HL2)Cl2(CH3OH)], complex (2), as the product while [In(HL2)Cl2]·CH3CH2OH, complex (3), was formed as the product using ethanol as solvent. Experimental data indicated that in complexes [In(HL2)Cl2(CH3OH)] (2) and [In(HL2)Cl2]·CH3CH2OH (3) one anionic ligand is attached to the indium(III) center through the O-Npy-N-O tetradentate chelating system along with two chlorides. The crystal structure of the complex [In(HL2)Cl2(CH3OH)] (2) revealed that the indium(III) center presents CN 7. Calculated bond lengths in complex (2) were in accordance with the experimental values. The experimental and calculated electronic spectra of complexes (1) and (2) presented the same pattern and allowed the attribution of the absorption peaks to π - π* transitions.

Coordination Polymers of Indium/Copper Selenolates and the Preparation of Metal Selenides

AbstractThe reactions of InCl3 with Na{Se(CH2)nNMe2} in 1:2 stoichiometry yielded complexes of composition [InCl{Se(CH2)nNMe2}2] (n=2 (1) or 3 (2)). Treatment of Me2InCl with Na(4‐SeC5H4N) afforded [Me2In(4‐SeC5H4N)]n (3). Copper complex [(PEt3)2Cu2(4‐SeC5H4N)2]n (4) was synthesized from CuCl, PEt3 and Na(4‐SeC5H4N). These complexes have been characterized by elemental analysis and NMR spectroscopy. Solid‐state structures of 3 and 4 revealed the formation of one‐ and two‐dimensional co‐ordination polymer which is formed via Se and N atoms of selenolate ligand. Thermal studies of these complexes have been carried out in a furnace or oleylamine to give thin film or nano‐materials of In2Se3, Cu1.8Se and CuInSe2.

Chemical synthesis of hexagonal indium nitride nanocrystallines at low temperature

In this study, hexagonal indium nitride nanocystallines with high crystallinity have been prepared by the reaction of InCl3·4H2O, sulfur and NaNH2 in an autoclave at 160°C. The crystal structures and morphologies of the obtained InN sample are characterized by X-ray diffraction and scanning electron microscope. As InCl3·4H2O is substituted by In(NO3)3·4.5H2O, InN nanocrystallines could also be obtained by using the similar method. The photoluminescence spectrum shows that the InN emits a broad peak positioned at 2.3eV.

Reaction of [formula omitted] ([formula omitted] = C6H3-2,6-(C6H2-2,4,6-Me3)2) with indium(I)chloride yields three m-terphenyl stabilized mixed-valent organoindium subhalides

Indium(I)chloride reacts with LiArMe6 (ArMe6=C6H3-2,6-(C6H2-2,4,6-Me3)2) in THF to give three new mixed-valent organoindium subhalides. While the 1:1 reaction of InCl with LiArMe6 yields the known metal-rich cluster In8(ArMe6)4 (1), the use of freshly prepared LiArMe6 led to incorporation of iodide, derived from the synthesis of LiArMe6, into the structures, to afford In4(ArMe6)4I2 (2) along with minor amounts of In3(ArMe6)3I2 (3). When the same reaction was performed in 4:3 stoichiometry, the mixed-halide compound In3(ArMe6)3ClI (4) was obtained. Further increasing the chloride:aryl ligand ratio resulted in the formation of the known mixed-halide species In4(ArMe6)4Cl2I2 that can also be obtained from the reaction of InCl with in situ prepared LiArMe6 in toluene. The new compounds 2 and 4 were characterized in the solid state by X-ray crystallography and IR spectroscopy, and in solution by UV/Vis and 1H/13C{1H} NMR spectroscopies. The structural characterization of 2 and 4 was supported by electronic structure calculations at the density functional level of theory which were also performed to rationalize the cluster-type bonding in 1.

Two novel indium coordination polymers derived from 2,6-pyridinedicarboxylate ligand: Syntheses, structures and photoluminescent properties

Two indium coordination polymers (CPs) with different structures InCl(2,6-pdc)(H2O) (1) and In2Cl4(2,6-pdc)(4,4′-bipy)2 (2) were synthesized by the reactions of InCl3 with 2,6-pyridinedicarboxylic acid (2,6-H2pdc) and 4,4′-bipyridine (4,4′-bipy) ligands. Compound 1 features a two dimensional (2D) network with the rhombic windows constructed from novel [In2O6(H2O)2Cl2(2,6-pdc)2] dimeric building units and 2,6-pdc2− ligands. Compound 2 possesses a 2D layer structure which is accomplished by connecting the wavy chains to the distorted 4,4′-bipy ligands. The different structures of 1 and 2 show the predominant influence of chlorine atoms and organic ligands. In addition, non-classical hydrogen-bond (C–H⋯Cl) interactions also play an important role in the formation of supramolecular architectures, for instance, to link 2D entities to 3D frameworks. These new In(III) CPs show intense fluorescence emission with long lifetimes in the solid state at room temperature.

Mononuclear and dinuclear indium(III) complexes containing methoxy and hydroxy-bridge groups, nitrate anion and 4,4′-dimethyl-2,2′-bipyridine ligand: synthesis, characterization, crystal structure determination, luminescent properties, and thermal analyses

[In(4,4′-dmbipy)(η2-NO3)2(η-NO3)(H2O)] complex (1) and [{In(4,4′-dmbipy)(η2-NO3)2}2(µ-OCH3)2] complex (2) (4,4′-dmbipy is 4,4′-dimethyl-2,2′-bipyridine) were prepared from the reaction of In(NO3)3·4H2O with 4,4′-dmbipy in CH3CN and CH3OH, respectively. [{In(4,4′-dmbipy)(η2-NO3)(η-NO3)}2(µ-OH)2] complex (3) was also prepared from the reaction of InCl3·4H2O with 4,4′-dmbipy in mixture of CH3CN/H2O in 3:1 ratio. These complexes were characterized by elemental analysis, IR, 1H NMR, 13C{1H}NMR, UV–Vis, and luminescence spectroscopy and their structures were studied by single-crystal X-ray diffraction method. Compound 1 is an eight-coordinated mononuclear complex, compound 2 is an eight-coordinated centrosymmetric dinuclear complex with two methoxy-bridges, and compound 3 is a seven-coordinated C2-symmetric dinuclear complex with two hydroxy-bridges. Also, the thermal stabilities of 1–3 were studied by thermogravimetric (TG) and differential thermal analyses (DTA).

ChemInform Abstract: Reaction of InCl3 with Various Reducing Agents: InCl3—NaBH4‐Mediated Reduction of Aromatic and Aliphatic Nitriles to Primary Amines.

AbstractNitriles containing halide moieties undergo tandem reduction giving dehalogenated amines such as (IV).

Synthesis of particulate InN crystal by the reaction of InCl3 with LiNH2

A method to synthesize indium nitride (InN) crystal by the reaction of InCl3 with LiNH2 under N2 atmosphere was studied. InN was formed at the temperature ranging from 350 to 450°C under 0.1 MPa N2 atmosphere. X-ray diffraction (XRD) pattern and transmission electron microscope (TEM) image indicated that synthesized InN was crystalline powder with a wurtzite structure. Band gap was determined by plotting (αhν)2 vs. hν for direct transition and the value of 0.83 eV was obtained.

Reaction of InCl3with Various Reducing Agents: InCl3–NaBH4-Mediated Reduction of Aromatic and Aliphatic Nitriles to Primary Amines

While alternative methods of preparing dichloroindium hydride (HInCl(2)) via the in situ reduction of InCl(3) using lithium amino borohydride (LAB) were explored, generation of HInCl(2) from the reduction of InCl(3) by sodium borohydride (NaBH(4)) was also re-evaluated for comparison. The reductive capability of the InCl(3)/NaBH(4) system was found to be highly dependent on the solvent used. Investigation by (11)B NMR spectroscopic analyses indicated that the reaction of InCl(3) with NaBH(4) in THF generates HInCl(2) along with borane-tetrahydrofuran (BH(3)·THF) in situ. Nitriles underwent reduction to primary amines under optimized conditions at 25 °C using 1 equiv of anhydrous InCl(3) with 3 equiv of NaBH(4) in THF. A variety of aromatic, heteroaromatic, and aliphatic nitriles were reduced to their corresponding primary amine in 70-99% isolated yields. Alkyl halide and nitrile functional groups were reduced in tandem by utilizing the reductive capabilities of both HInCl(2) and BH(3)·THF in a one-pot reaction. Finally, the selective reduction of the carbon bromine bond in the presence of nitriles was achieved by generating HInCl(2) via the reduction InCl(3) with NaBH(4) in CH(3)CN or with lithium dimethylaminoborohydride (MeLAB) in THF.

Preparation and structure of an enantiomeric water-bridged dinuclear indium complex containing two homochiral N atoms and its performance as an initiator in polymerization of rac-lactide

Abstract A novel dinuclear indium complex (1) containing a sole water bridge was prepared from the reaction of InCl3 with an unsymmetric N2O2-ligand and the molecular structure of the complex 1 was determined. The X-ray crystallography data show that the dinuclear complex possesses two homochiral N atoms, namely, N(R)N(R) and N(S)N(S) enantiomers. Complex 1 was used as initiator for ring-opening polymerization of rac-lactide, giving heterotactic-rich polylactide (Pr = 0.63–0.69) with narrow polydispersities (1.13–1.31).

Synthesis, characterization and biological evaluation of In(iii) complexes anchored by DOTA-like chelators bearing a quinazoline moiety

Following previous studies with a DOTA-like bifunctional chelator (H(3)L1) containing an ethylenic linker between the macrocycle backbone and a quinazoline pharmacophore, we synthesized and fully characterized a congener macrocyclic ligand (H(3)L2) having a longer, five-carbon spacer for the linkage of the quinazoline moiety. Both H(3)L1 and H(3)L2 were used to prepare indium(III) complexes aiming at their evaluation as radioactive probes for in vivo targeting of EGFR-TK. The protonation constants (log K(Hi)) of H(3)L2 were determined by potentiometry and UV-Vis spectrophotometry and the values found are 12.18, 9.74, 4.99, 3.91 and 2.53. The stability and protonation constants of InL (L = L1, L2) were also obtained from a combined potentiometry and UV-VIS spectrophotometry study. The reaction of InCl(3) with H(3)L1 and H(3)L2 led to the formation of the well-defined complexes InL1 and InL2, containing In(iii) ions coordinated by a seven (N(4),O(3)) donor atom set. These new complexes were fully characterized by spectroscopic methods (IR, NMR, ESI-MS), HPLC and by X-ray diffraction analysis in the case of InL1. The radioactive congener (111)InL2 was prepared from the reaction of (111)In-chloride with H(3)L2, in high yield and high radiochemical purity. (111)InL2 is a neutral complex that presents a hydrophilic character and exhibits a high in vitro and in vivo stability. H(3)L2 and InL2 do not inhibit the cell growth of A431 cervical carcinoma cells. In this EGFR-expressing cell line, (111)InL2 has shown very low cell internalization. These findings indicate that these DOTA-like chelators are not the best suited bifunctional ligands to obtain In(iii) complexes with adequate biological properties for targeting the EGFR-TK.

Polymorphism of In5S5Cl – X‐ray and HRTEM‐Investigations

AbstractIn5S5Cl belongs to the group of mixed valence indium compounds with indium occurring simultaneously in three oxidation states (In5S5Cl = In+(In2)4+2In3+5S2–Cl–). It was shown in an earlier work that In5S5Cl obtained from InCl3, indium and sulfur at 550 °C, crystallises in a monoclinic structure type in contrast to the orthorhombic bromide, In5S5Br. The main difference of both structure types is an ordered mutual exchange of In+ and (In2)4+ in specific crystallographic positions. This exchange is possible due to the almost identical coordination pattern of both ions. A closer inspection of the real structure of monoclinic In5S5Cl by High Resolution Transmission Microscopy (HRTEM) already showed the presence of small orthorhombic domains in the real structure of this compound. Now we also obtained macroscopic quantities of orthorhombic In5S5Cl by the reaction of InCl3, indium and sulfur at reaction temperatures below 500 °C (Pmn21, a = 3.907(1) Å, b = 9.021(2) Å, c = 14.866(3) Å, Z = 2). The new polymorph is analysed by X‐ray single crystal and X‐ray powder diffraction and HRTEM investigations.

Syntheses and crystal structures of the homoleptic [Et 4N][M(SC 6H 4Me- p) 4] (M = Ga, In) and [Et 4N][Ga(SePh) 4

Treatment of [Et 4N][GaCl 4] with four equivalents of NaQR in methanol afforded the substitution complexes [Et 4N][Ga(QR) 4] (QR = SC 6H 4Me- p 1, QR = SePh 3), while the indium analogues [Et 4N][In(SC 6H 4Me- p) 4] ( 2) was prepared by the reaction of InCl 3·3H 2O and NaSC 6H 4Me- p in the presence of [Et 4N]Cl· xH 2O. The structures of these three complexes, as determined by single-crystal X-ray diffraction, feature well-separated cations and anions with the metal centers of the anions tetrahedrally coordinated to four thiolate or selenolate ligands. The thermal stability of the three complexes was studied by thermal gravimetric analysis.

Synthesis and Structures of New Copper‐Indium Thiolate Cluster Complexes

AbstractTwo new copper indium thiolate complexes were obtained from the reactions of InCl3 and HSnBu with a combination of [Cu(NCMe)4][PF6] and 1,2‐bis(diphenylphosphino)ethane (dppe). In a mixture of methanol and MeCN solvent the complex [In2SnBu2(μ‐SnBu)2Cu2(μ‐dppe)2] (3) was formed. When this reaction was performed in a mixture of MeOH and CH2Cl2 solvent, a higher nuclearity species, [Cu(dppe)2][In4Cl4(μ‐SnBu)12Cu4(μ4‐Cl)] (4) was formed. The monoanion in 4 consists of a central tetrahedral chloride ion coordinated to four copper atoms. The copper atoms are linked to four outer InCl groups by three bridging butylthiolato ligands. Overall, this ion has approximate T‐symmetry and is chiral.

New 3-D Chiral Framework of Indium with 1,3,5-Benzenetricarboxylate

A new complex, [In(2)(mu-OH)(2)(btc)(2)](n)().2nHpy (1) (btc = 1,3,5-benzenetricarboxylate; py = pyridine), is hydrothermally synthesized from the reaction of InCl(3), H(3)btc, and pyridine. Complex 1 crystallizes in the monoclinic P2(1) space group [a = 7.3181(12) A, b = 17.0195(23) A, c = 10.5789(17) A, beta = 102.651(6) degrees , and Z = 2]. Indium(III) centers in 1 are bridged by btc ligands in various coordination modes to form the nonclose rings which are further interlinked along crystallographic a-axis and (011) plane to result in a nonpenetrated 3-D anionic framework growing as homochiral tunnels. Compound 1 is fully characterized by fluorescence spectroscopy, second harmonic generation measurement, infrared, and thermogravimetric analysis.

Heterobimetallic heterocyclic derivatives of indium(III)

AbstractReactions of InCl3 with potassium salts of bifunctional tridentate (L1H2HOC6H4CH NCH2CHMeOH) and monofunctional bidentate (L2HHOC6H4CHN‐i‐Bu) Schiff bases in 1:1 and 1:2 molar ratio in benzene afford complexes In(L1)Cl and In(L2)2Cl, respectively. On reaction with potassium isopropoxymetallates KB(O‐i‐Pr)4, KAl(O‐i‐Pr)4, KTi(O‐i‐Pr)5, and KNb(O‐i‐Pr)6, they produce interes‐ ting heterobimetallic heterocyclic complexes. These are characterized by elemental (N, B, Al, Ti, and Nb) analyses, molecular weight measurements, and spectral [IR, NMR (1H, 13C, 11B, and 27Al)] studies. Probable structures are suggested for them. © 2003 Wiley Periodicals, Inc. 15:21–25, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/.hc10206

Kinetically Controlled Solid State Reactions in the System InCl/SnCl2

AbstractThis paper reports on studies on the reaction of InCl with SnCl2 to form ternary halides. The reaction route is investigated by x‐ray investigations at different temperatures. Depending on the modification of InCl as educt and on the temperature conditions the reaction follows different pathways which may include intermediate redox reactions of the type In+ + Sn2+ → In3+ + Sn0.

Thermodynamics and phase stability in the In–N system

Results of a chemical vapor deposition crystal growth method intended to produce large amounts of InN needed for thermodynamic experiments are reported. Polycrystalline films of InN were grown by reaction of InCl3 and NH3 in a hot-wall silica reactor under nearly atmospheric pressure. Samples were analyzed using x-ray diffraction and chemical analysis. The decomposition of InN was studied in both thin film and powder form. InN films were investigated by isothermal heating under nitrogen and subsequent microscopic inspection. The removal of the nucleation barrier of forming the first liquid phase was emphasized. InN powder decomposition experiments involved two different customized thermogravimetric methods: (i) dynamic oscillation thermogravimetric analysis (TGA), and (ii) isothermal stepping TGA for a higher resolution of the decomposition start. The decomposition start was found consistently at (773 ±5) K under 1 bar of nitrogen. Nevertheless, it is suggested that InN may be metastable even below room temperature based on Computer Coupling of Phase Diagrams and Thermo chemistry-type thermodynamic analysis of all available phase equilibrium and thermodynamic data. This included the determination of the absolute entropy of InN, 31.6 ±3 J/mol-formula K, based on a Debye and Einstein analysis of the experimental data on the heat capacity. All calculations of pressure are corrected for the fugacity of nitrogen, which becomes crucial above 1000 bar. The contradictory literature data in the In–N system are discussed based on three different internally consistent thermodynamic analyses of the system that highlight the consequences of different choices made on the decomposition temperature of InN. Widely reproduced data in the literature are shown to produce thermodynamically impossible negative absolute entropy of InN. Complete P-T-x phase diagrams are given, which strongly suggest that solid InN is metastable under ambient conditions. To find out that InN crystals could be reproducibly superheated more than 500 K before they actually decompose comes as a surprise compared to other III-V systems, especially Ga–N.

Preparation of InN nanocrystals by solvo-thermal method

Indium nitride (InN) nanocrystals were successfully prepared by the reaction of InCl3 and Li3N at 250°C with xylene as the solvent. X-ray powder diffraction and TEM observation showed that the two phases of cubic InN and hexagonal InN coexist in the nanocrystals prepared by the solvo-thermal method.

Cationic Indium Alkyl Complexes Incorporating Aminotroponiminate Ligands

The synthesis and structures of indium complexes incorporating the bidentate monoanionic ligand N,N‘-diisopropylaminotroponiminate (iPr2-ATI) are described. The reaction of InCl3 with Li[iPr2-ATI] yields (iPr2-ATI)InCl2 (3), which is converted to (iPr2-ATI)InMe2 (4) by reaction with MeLi; 4 is also formed by the reaction of InMe3 with (iPr2-ATI)H. The reaction of 4 with [Ph3C][B(C6F5)4] at 23 °C yields the diimine complex [{1,2-(NiPr)2-5-CPh3-cyclohepta-3,6-diene}InMe2][B(C6F5)4] (5) via addition of Ph3C+ to the C5 carbon of 4. Thermolysis of 5 (75 °C) yields [(iPr2-ATI)InMe][B(C6F5)4] (6) and Ph3CMe. 6 was isolated as the chlorobenzene solvate 6·PhCl. An X-ray diffraction study shows that there are two independent cations in the asymmetric unit of 6·PhCl. One cation (In(1)) is ion-paired with two B(C6F5)4- anions, while the second cation is complexed with two PhCl molecules and is disordered between two equally occupied positions (In(2) and In(3)). Dative In−ClPh bonding and PhCl/ATI π-stacking interactions contribute to the PhCl coordination in 6·PhCl. The reaction of 4 with B(C6F5)3 yields [(iPr2-ATI)InMe][MeB(C6F5)3] (7), which decomposes slowly at 23 °C by C6F5- transfer reactions. The reaction of 4 with [HNMe2Ph][B(C6F5)4] yields the labile amine adduct [(iPr2-ATI)In(Me)(NMe2Ph)][B(C6F5)4] (10).