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1.
Inorg Chem ; 61(9): 4018-4023, 2022 Mar 07.
Artículo en Inglés | MEDLINE | ID: mdl-35202543

RESUMEN

The novel tin(II) oxychloride [BMIm][Sn5O2Cl7] (BMIm = 1-butyl-3-methylimidazolium) is obtained by the room-temperature reaction (25 °C) of black SnO and SnCl2 in [BMIm]Cl/SnCl2 as an ionic liquid. The title compound can be described as composed of noncharged, infinite ∞1(Sn2OCl2) strands that are embedded in a saline matrix of [BMIm]+ and [SnCl3]-. The ∞1(Sn2OCl2) strands consist of a backbone of edge-sharing OSn4/2 tetrahedra, which represent one-dimensional (1D) strands cut out of the layer-type structure of SnO. In [BMIm][Sn5O2Cl7], the ∞1(Sn2OCl2) strands, which mimic a 1D semiconductor, are terminated by chlorine atoms, whereas they are interconnected by oxygen atoms in the 2D semiconductor SnO. The view of the noncharged ∞1(Sn2OCl2) strands in a saline [BMIm][SnCl3] matrix is validated by dissolution experiments. Thus, electron microscopy and Raman spectroscopy show a deconstruction of [BMIm][Sn5O2Cl7] single crystals after treatment with chloroform with a dissolution of [BMIm][SnCl3], the formation of SnCl2 needles, and tin oxide as a solid remain.

2.
J Am Chem Soc ; 143(2): 798-804, 2021 Jan 20.
Artículo en Inglés | MEDLINE | ID: mdl-33405904

RESUMEN

The crown-ether coordination compounds ZnX2(18-crown-6), EuX2(18-crown-6) (X: Cl, Br, I), MnI2(18-crown-6), Mn3Cl6(18-crown-6)2, Mn3I6(18-crown-6)2, and Mn2I4(18-crown-6) are obtained by ionic-liquid-based synthesis. Whereas MX2(18-crown-6) (M: Zn, Eu) show conventional structural motives, Mn3Cl6(18-crown-6)2, Mn3I6(18-crown-6)2, and Mn2I4(18-crown-6) exhibit unusual single MnX4 tetrahedra coordinated to the crown-ether complex. Surprisingly, some compounds show outstanding photoluminescence. Thus, rare Zn2+-based luminescence is observed and unexpectedly efficient for ZnI2(18-crown-6) with a quantum yield of 54%. Unprecedented quantum yields are also observed for Mn3I6(18-crown-6)2, EuBr2(18-crown-6), and EuI2(18-crown-6) with values of 98, 72, and 82%, respectively, which can be rationalized based on the specific structural features. Most remarkable, however, is Mn2I4(18-crown-6). Its specific structural features with finite sensitizer-activator couples result in an extremely strong emission with an outstanding quantum yield of 100%. Consistent with its structural features, moreover, anisotropic angle-dependent emission under polarized light and nonlinear optical (NLO) effects occur, including second-harmonic generation (SHG). The title compounds and their optical properties are characterized by single-crystal structure analysis, X-ray powder diffraction, chemical analysis, density functional theory (DFT) calculations, and advanced spectroscopic methods.

3.
Inorg Chem ; 60(20): 15653-15658, 2021 Oct 18.
Artículo en Inglés | MEDLINE | ID: mdl-34614358

RESUMEN

GaSeCl5O is a new inorganic molecular compound prepared from SeO2, SeCl4, and GaCl3 at 50 °C in quantitative yield. The structure of the title compound is described by GaCl3(OSeCl2) molecules with a tetrahedrally coordinated Ga atom and a pseudo-tetrahedrally coordinated Se atom (including lone pair of Se(IV)) that are bridged by oxygen. GaSeCl5O crystallizes in the polar chiral space group P61, which is rarely observed for molecular structures. The compound is characterized by X-ray structure analysis based on single crystals and powder samples, thermogravimetry, infrared and Raman spectroscopy as well as by second harmonic generation (SHG) measurements. The experimental data are complemented by density functional theory calculations. GaSeCl5O shows one of the strongest SHG signals known in the visible part of the electromagnetic spectrum (480-700 nm) with an SHG intensity 10 times higher than potassium dihydrogen phosphate (KDP). This is in accordance with the phase matchability and a strong dipole moment (|µ| = 8.3 D for a molecule in the crystal lattice). Such a strong SHG effect is also remarkable since GaSeCl5O-unlike most of the materials with strong SHG intensity-is an inorganic molecular compound.

4.
Inorg Chem ; 59(17): 12895-12902, 2020 Sep 08.
Artículo en Inglés | MEDLINE | ID: mdl-32845616

RESUMEN

Orange, transparent crystals of [BMIm]2[Mn(CO)3(GeI3)3] (BMIm: 1-butyl-3-methylimidazolium) are obtained by reacting GeI4, [Mn(CO)6][AlCl4], and Ph3GeH in the ionic liquid [BMIm][NTf2]. [Mn(CO)6][AlCl4] and triphenylgermane turn out to be essential as reactive carbonyl precursors and for the reduction of GeI4. According to X-ray structure analysis based on single crystals, the title compound exhibits a novel {MnGe3} cluster unit with Mn-Ge single bonds and surprisingly short distances (236-241 pm). Although sensitive to oxygen/moisture, the carbonyl compound is stable up to a temperature of 150 °C. Mass spectrometry (MS) shows [Mn(CO)3(GeI3)2]-, [Mn(CO)3(GeI3)I]-, and [GeI3]- as decomposition fragments in the gas phase. In addition to crystal structure analysis and MS, the title compound is characterized by energy-dispersive X-ray spectroscopy (EDXS), thermogravimetry (TG), optical spectroscopy (UV-visible), infrared spectroscopy (FT-IR), and density functional theory (DFT) calculations.

5.
Angew Chem Int Ed Engl ; 59(14): 5510-5514, 2020 Mar 27.
Artículo en Inglés | MEDLINE | ID: mdl-31774935

RESUMEN

[SnI8 {Fe(CO)4 }4 ][Al2 Cl7 ]2 contains the [SnI8 {Fe(CO)4 }4 ]2+ cation with an unprecedented highly coordinated, bicapped SnI8 prism. Given the eightfold coordination with the most voluminous stable halide, it is all the more surprising that this SnI8 arrangement is surrounded only by fragile Fe(CO)4 groups in a clip-like fashion. Inspite of a predominantly ionic bonding situation in [SnI8 {Fe(CO)4 }4 ]2+ , the I- ⋅⋅⋅I- distances are considerably shortened (down to 371 pm) and significantly less than the van der Waals distance (420 pm). The title compound is characterized by single-crystal structure analysis, spectroscopic methods (EDXS, FTIR, Raman, UV/Vis, Mössbauer), thermogravimetry, and density functional theory methods.

6.
Angew Chem Int Ed Engl ; 55(51): 15728-15752, 2016 12 19.
Artículo en Inglés | MEDLINE | ID: mdl-27862742

RESUMEN

Microemulsions (MEs) are ideal for obtaining high-quality inorganic nanoparticles. As thermodynamically stable systems with a nanometer-sized droplet phase that serves as a nanoreactor, MEs have obvious advantages for the synthesis of nanoparticles. MEs also have disadvantages, such as their complexity as multicomponent systems, the low amount of obtainable nanoparticles, their limited thermal stability, the fact that hydrolyzable or oxidizable compounds are often excluded from synthesis, the partly elaborate separation of nanoparticles, as well as the removal of surface-adhered surfactants subsequent to synthesis. This Review presents some strategies to further expand the options of ME-based synthesis of inorganic nanoparticles. This comprises the crystallization of nanoparticles in "high-temperature MEs", the synthesis of hollow nanospheres, the use of hydrogen peroxide or liquid ammonia as the polar droplet phase, and the synthesis of base metals and nitrides in MEs.

7.
Inorg Chem ; 54(8): 3989-94, 2015 Apr 20.
Artículo en Inglés | MEDLINE | ID: mdl-25830920

RESUMEN

[BMIm]2[{PbMn(CO)5)}6I8] (BMIm: 1-butyl-3-methylimidazolium) is obtained by ionic liquid mediated reaction of PbI2 and Mn2(CO)10. Central is a cubelike (Pb6I8) unit containing a nonfilled Pb6 octahedron. Each Pb of this (Pb6I8) unit is terminated on its outside by Mn(CO)5, exhibiting Pb-Mn metal-to-metal bonding (280 pm). Structurally, the (Pb6I8) unit is similar to the well-known octahedral (M6Xn) cluster-type family (M = Zr, Nb, Ta, Mo, W; X = Cl, Br, I). In contrast to most similar cluster compounds, such as W6Br12 ([W6Br8]Br2/1Br4/2, according to Niggli notation) or the carbonyl cluster [Sn6{Cr(CO5)6}](2-), however, the nonfilled central Pb6 octahedron in [{PbMn(CO)5)}6I8](2-) does not exhibit any metal-to-metal bonding. Structure and bonding of the title compound are validated by single-crystal structure analysis, energy-dispersive X-ray analysis (EDX), infrared spectroscopy (FT-IR), and density functional theory (DFT) calculations. Based on the isolobal principle, electronegativity considerations, bond lengths, and DFT calculations including Mulliken population analysis and natural population analysis (NPA), in sum, the charge distribution of Pb is best reflected by an oxidation state of +1.

8.
Adv Sci (Weinh) ; 11(21): e2309043, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38509846

RESUMEN

The carbonyl cluster compound [GeRu6(CO)18HI] is unique in regard to its structure and bonding with a GeRu6 cluster core, a planar GeRu4HI unit, extensive multi-center bonding, and an aromatic ring current similar to benzene (9-10 nA T-1). The open-shell cluster core is a Ge-centered five-membered Ru4(Ru2) ring with CO ligands and an additional H and I atom, each bridging two Ru atoms on opposite sides of the cluster core. The compound is prepared at 130 °C in a weakly-coordinating ionic liquid.

9.
Chem Commun (Camb) ; 59(74): 11113-11116, 2023 Sep 14.
Artículo en Inglés | MEDLINE | ID: mdl-37646079

RESUMEN

The pseudo-ternary tin(II) halide [BMPyr]2[SnCl4] can be obtained just by mixing the starting materials [BMPyr]Cl and SnCl2 at room temperature without additional solvents. The compound shows bright Sn(II)-based emission of deep-red light (λmax: 740 nm) with a quantum yield of 88 ± 3% after optimised synthesis. Characterization is performed by X-ray structure analysis, infrared and fluorescence spectroscopy. Exemplary fluorescent thinfilms are realized by solvent processing.

10.
ChemistryOpen ; 12(2): e202200226, 2023 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-36811286

RESUMEN

The novel tin bromido aluminates [Sn3 (AlBr4 )6 ](Al2 Br6 ) (1), Sn(AlBr4 )2 (2), [EMIm][Sn(AlBr4 )3 ] (3) and [BMPyr][Sn(AlBr4 )3 ] (4) ([EMIm]: 1-ethyl-3-methylimidazolium, [BMPyr]: 1-butyl-1-methyl-pyrrolidinium), are obtained from a ionic-liquid-based reaction of AlBr3 and SnCl2 or SnBr2 , resulting in colorless and transparent crystals. 1 contains a neutral, inorganic ∞ 3 [Sn3 (AlBr4 )6 ] network filled with intercalated Al2 Br6 molecules. 2 represents a 3D structure isotypic to Pb(AlCl4 )2 or α-Sr[GaCl4 ]2 . 3 and 4 exhibit infinite ∞ 1 [Sn(AlBr4 )3 ]n- chains that are separated by the voluminous [EMIm]+ /[BMPyr]+ cations. All title compounds contain Sn2+ coordinated by AlBr4 tetrahedra, resulting in chains or 3D networks. Moreover, all title compounds show photoluminescence due to Br- →Al3+ ligand-to-metal charge-transfer excitation, followed by 5s2 p0 ←5s1 p1 emission on Sn2+ . Most surprisingly, the luminescence is highly efficient (quantum yield >50 %). Specifically, 3 and 4 exhibit outstanding quantum yields of 98 and 99 %, which are the highest values observed for Sn2+ -based luminescence so far. The title compounds have been characterized by single-crystal structure analysis, elemental analysis, energy-dispersive X-ray analysis, thermogravimetry, infrared and Raman spectroscopy, UV-Vis and photoluminescence spectroscopy.

11.
Chemistry ; 18(43): 13600-4, 2012 Oct 22.
Artículo en Inglés | MEDLINE | ID: mdl-22987543

RESUMEN

Show some metal: the first bimetallic adamantane-like cluster, [{Fe(CO)(3)}(4){SnI}(6)I(4)](2-), was prepared by an ionic-liquid-based synthesis. The valence states of iron and tin were verified based on bond-length considerations, FT-IR and (119)Sn Mössbauer spectroscopy, as well as with DFT calculations.


Asunto(s)
Adamantano/química , Compuestos Organometálicos/química , Estaño/química , Cristalografía por Rayos X , Líquidos Iónicos/química , Hierro/química , Conformación Molecular , Espectroscopía Infrarroja por Transformada de Fourier , Espectroscopía de Mossbauer
12.
Angew Chem Int Ed Engl ; 50(47): 11050-60, 2011 Nov 18.
Artículo en Inglés | MEDLINE | ID: mdl-21990270

RESUMEN

Ionic liquids are credited with a number of unusual properties. These include a low vapor pressure, a wide liquid-phase range, weakly coordinating properties, and a high thermal/chemical stability. These properties are certainly of great interest for inorganic synthesis and the creation of novel inorganic compounds. On the other hand, the synthesis repertoire for preparing inorganic compounds has always been broad, ranging from syntheses in solutions and melts to solid-state reactions, and from crystal growth in the gas phase to high-pressure syntheses. What new aspects can ionic liquids then add to the synthesis of inorganic compounds? This Minireview uses some early examples to show that the use of ionic liquids indeed provides access to unusual inorganic compounds.

13.
Dalton Trans ; 50(24): 8549-8557, 2021 Jun 22.
Artículo en Inglés | MEDLINE | ID: mdl-34075928

RESUMEN

[BMIm][Sn(AlCl4)3] (1) ([BMIm]: 1-butyl-3-methylimidazolium), [BMPyr][Sn(AlCl4)3] (2) ([BMPyr]: 1-butyl-1-methyl-pyrrolidinium), and [BMIm][Pb(AlCl4)3] (3) are obtained by reaction of SnCl2/PbCl2 in [BMIm]Cl/[BMPyr]Cl/AlCl3-based ionic liquids. The colourless crystals of the title compounds contain infinite 1∞[M(AlCl4)3]n- chains (M: Sn, Pb) that are separated by the voluminous [BMIm]+/[BMPyr]+ cations. The central Sn2+/Pb2+ is coordinated by chlorine in the form of distorted squared anti-prismatic polyhedra. Each Cl atom, in turn, is part of an [AlCl4]- tetrahedron that interlinks Sn2+/Pb2+ to the chain-like building unit. In addition to the novel structural arrangement, all title compounds surprisingly show intense white-light emission. Although Sn2+ and Pb2+ are well-known as dopants in conventional phosphors, efficient luminescence via s-p-transitions of compounds containing Sn2+/Pb2+ in molar quantities and as regular lattice constituents is rare. The emission of [BMIm][Sn(AlCl4)3] and [BMPyr][Sn(AlCl4)3] is very efficient with quantum yields of 51 and 76%, which belong to the highest values known for s-p-based luminescence of Sn2+.

14.
Front Neurol ; 12: 675255, 2021.
Artículo en Inglés | MEDLINE | ID: mdl-34177780

RESUMEN

A better understanding of motor recovery after stroke requires large-scale, longitudinal trials applying suitable assessments. Currently, there is an abundance of upper limb assessments used to quantify recovery. How well various assessments can describe upper limb function change over 1 year remains uncertain. A uniform and feasible standard would be beneficial to increase future studies' comparability on stroke recovery. This review describes which assessments are common in large-scale, longitudinal stroke trials and how these quantify the change in upper limb function from stroke onset up to 1 year. A systematic search for well-powered stroke studies identified upper limb assessments classifying motor recovery during the initial year after a stroke. A metaregression investigated the association between assessments and motor recovery within 1 year after stroke. Scores from nine common assessments and 4,433 patients were combined and transformed into a standardized recovery score. A mixed-effects model on recovery scores over time confirmed significant differences between assessments (P < 0.001), with improvement following the weeks after stroke present when measuring recovery using the Action Research Arm Test (ß = 0.013), Box and Block test (ß = 0.011), Fugl-Meyer Assessment (ß = 0.007), or grip force test (ß = 0.023). A last-observation-carried-forward analysis also highlighted the peg test (ß = 0.017) and Rivermead Assessment (ß = 0.011) as additional, valuable long-term outcome measures. Recovery patterns and, thus, trial outcomes are dependent on the assessment implemented. Future research should include multiple common assessments and continue data collection for a full year after stroke to facilitate the consensus process on assessments measuring upper limb recovery.

15.
ChemistryOpen ; 10(2): 171-180, 2021 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-33565722

RESUMEN

Nine Ge-Fe carbonyl cluster compounds are prepared via ionic liquids-based synthesis. This includes the novel compounds [EMIm][Fe(CO)3 I(GeI3 )], [EHIm][Fe(CO)3 I(GeI3 )], [BMIm][GeI2 {Fe(CO)4 }2 (µ-I)][AlCl4 ]2 , [GeI2 {Fe(CO)4 }2 (µ-I)][Fe(AlBr4 )3 ], [BMIm]2 [(FeI2 )0.75 {Fe(CO)2 I(GeI3 )2 }2 ], and [EHIm][Fe(CO)4 (GeI2 )2 Fe(CO)3 GeI3 ] as well as the previously reported compounds (Fe(CO)4 (GeI3 )2 , FeI4 {GeI3 Fe(CO)3 }2 , and Ge12 {Fe(CO)3 }8 (µ-I)4 (EMIm: 1-ethyl-3-methylimidazolium, EHIm: 1-ethylimidazolium, BMIm: 1-butyl-3-methylimidazolium). With this series of compounds, a comparison of synthesis conditions and structural features is possible and, for instance, allows correlating the composition and structure of the respective Ge-Fe carbonyl cluster compounds with the type and acidity of the ionic liquid. With [EMIm][{GeI3 }2 Fe(CO)3 I], moreover, we can exemplarily show the thermal decomposition as a single-source precursor in the ionic liquid, resulting in bimetallic Ge-Fe nanoparticles with small size and narrow size distribution (7.0±1.4 nm).

16.
Neurol Res Pract ; 3(1): 66, 2021 Dec 27.
Artículo en Inglés | MEDLINE | ID: mdl-34955097

RESUMEN

BACKGROUND: Impaired motor functions after stroke are common and negatively affect patients' activities of daily living and quality of life. In particular, hand motor function is essential for daily activities, but often returns slowly and incompletely after stroke. However, few data are available on the long-term dynamics of motor recovery and self-reported health status after stroke. The Interdisciplinary Platform for Rehabilitation Research and Innovative Care of Stroke Patients (IMPROVE) project aims to address this knowledge gap by studying the clinical course of recovery after inpatient rehabilitation. METHODS: In this prospective observational longitudinal multicenter study, patients were included towards the end of inpatient rehabilitation after ischemic or hemorrhagic stroke. Follow-up examination was performed at three, six, and twelve months after enrollment. Motor function was assessed by the Upper Extremity Fugl-Meyer Assessment (FMA), grip and pinch strength, and the nine-hole peg test. In addition, Patient-Reported Outcomes Measurement Information System 10-Question Short Form (PROMIS-10) was included. Linear mixed effect models were fitted to analyze change over time. To study determinants of hand motor function, patients with impaired hand function at baseline were grouped into improvers and non-improvers according to hand motor function after twelve months. RESULTS: A total of 176 patients were included in the analysis. Improvement in all motor function scores and PROMIS-10 was shown up to 1 year after inpatient rehabilitation. FMA scores improved by an estimate of 5.0 (3.7-6.4) points per year. In addition, patient-reported outcome measures increased by 2.5 (1.4-3.6) and 2.4 (1.4-3.4) per year in the physical and mental domain of PROMIS-10. In the subgroup analysis non-improvers showed to be more often female (15% vs. 55%, p = 0.0155) and scored lower in the Montreal Cognitive Assessment (25 [23-27] vs. 22 [20.5-24], p = 0.0252). CONCLUSIONS: Continuous improvement in motor function and self-reported health status is observed up to 1 year after inpatient stroke rehabilitation. Demographic and clinical parameters associated with these improvements need further investigation. These results may contribute to the further development of the post-inpatient phase of stroke rehabilitation. TRIAL REGISTRATION: The trial is registered at ClinicalTrials.gov (NCT04119479).

17.
Neurol Res Pract ; 2: 10, 2020.
Artículo en Inglés | MEDLINE | ID: mdl-33324916

RESUMEN

INTRODUCTION: Stroke and its long-term consequences pose major challenges for the lives of those affected and healthcare systems. Neurological rehabilitation therefore primarily attempts to improve function in order to increase independence in activities of daily living, and to enable social participation. There is only scarce data on dynamics of functional recovery after patients discharge from inpatient neurological rehabilitation. Even less is known about the patient's perspective on long-term recovery from stroke. The Interdisciplinary Platform for Rehabilitation Research and Innovative Care of Stroke Patients (IMPROVE) aims to address this knowledge gap by providing new insights into the dynamics and extent of functional recovery from stroke beyond inpatient rehabilitation treatment. METHODS: We provide the protocol for an observational, longitudinal, multicenter study conducted in an Universitary Stroke Center in cooperation with five Neurological Rehabilitation Centers in Northern Germany. Patients who suffered from ischemic or hemorrhagic stroke will be enrolled by the end of inpatient rehabilitation and followed up to 1 year. In addition, a group of chronic stroke patients and a group of craniocerebral trauma patients will be enrolled as a comparison group. Data on stroke characteristics, vascular risk factors, co-morbidities, social support, and demographics will be recorded. Comprehensive clinical evaluation will be performed at baseline, three, six, and twelve months after enrollment. The assessments and scores used reflect the three components of the International Classification of Functioning, Disability and Health (ICF), some of them are tests regularly used in rehabilitation settings. Tests of motor function, cognition, and mood are included, as are tests of self-reported health-related quality of life. Primary outcome measure is a hand motor score, built by the sum of the hand items of the Fugl-Meyer Assessment as an objective measurement of hand function at 12 months after enrollment. Predictors of the primary outcome will be analyzed using linear regression analysis. PERSPECTIVE: The results of IMPROVE will inform about the long-term dynamics of functional stroke recovery after patients' discharge from inpatient rehabilitation and will provide insights into the association of clinical and demographic factors with recovery of function. TRIAL REGISTRATION: The protocol is registered at ClinicalTrials.gov (NCT04119479).

18.
Dalton Trans ; 48(41): 15521-15528, 2019 Oct 22.
Artículo en Inglés | MEDLINE | ID: mdl-31310261

RESUMEN

The novel tellurium rhenium carbonyls [TeI2Re(CO)5][AlCl4] (1), [BMIm][Te2I4(µ-I)2Re(CO)4] (2), {Te3I2(µ-I)3(µ3-I)}Re(CO)3 (3) and [BMIm][(Te2)3{Re(CO)3}2{Re(CO)4}3] (4) were prepared by reacting TeI4 and Re2(CO)10 in ionic liquids (ILs). [TeI2Re(CO)5][AlCl4] (1) was obtained in a mixture of [BMIm]Cl (BMIm: 1-butyl-3-methylimidazolium) and AlCl3 (ratio: 1 : 1) and contains a [TeI2Re(CO)5]+ cation. Increasing the amount of AlCl3 ([BMIm]Cl : AlCl3 = 1 : 2) results in [BMIm][Te2I4(µ-I)2Re(CO)4] (2) with the anion [Te2I4(µ-I)2Re(CO)4]-. At a [BMIm]Cl to AlCl3 ratio of 1 : 3, {Te3I2(µ-I)3(µ3-I)}Re(CO)3 (3) was realized with a Te3I3 ring and µ3-coordinating iodine. Finally, [BMIm][(Te2)3{Re(CO)3}2{Re(CO)4}3] (4) was prepared in [BMIm][OTf] (OTf: triflate) and contains the ufosan-like anion [(Te2)3{Re(CO)3}2{Re(CO)4}3]- with three Te22- and two Re(CO)3+ units that establish a distorted heterocuban-like cage. The compounds were characterized by single-crystal structure analysis, energy dispersive X-ray (EDX) analysis, thermogravimetry (TG), and infrared spectroscopy (FT-IR). The course of the reaction and the formation of the four novel tellurium-rhenium carbonyls can be directly correlated to the reaction conditions and especially to the acidity of the IL.

19.
Dalton Trans ; 48(14): 4696-4701, 2019 Apr 02.
Artículo en Inglés | MEDLINE | ID: mdl-30895999

RESUMEN

[Pb{Mn(CO)5}3][AlCl4] containing a trigonal planar PbMn3 cluster was obtained by the reaction of PbCl2 and Mn2(CO)10 in the ionic liquid [BMIm][AlCl4]. The title compound is composed of [Pb{Mn(CO)5}3]+ carbonyl cations and [AlCl4]- anions that are connected to infinite zig-zag chains. The [Pb{Mn(CO)5}3]+ cation exhibits a central PbMn3 cluster with three equal Pb-Mn single bonds, resulting in an almost equilateral triangle of three manganese atoms with a formal Pb+I in its center. Such a cluster and compound were identified for the first time. In addition to single-crystal structure analysis, the composition, structure and properties were further characterized by density functional theory (DFT) calculations, energy dispersive X-ray spectroscopy (EDXS), and Fourier-transform infrared spectroscopy (FT-IR), as well as optical spectroscopy (UV-Vis).

20.
Chem Commun (Camb) ; 54(10): 1217-1220, 2018 Jan 31.
Artículo en Inglés | MEDLINE | ID: mdl-29336437

RESUMEN

The germanium-iron cluster Ge12{Fe(CO)3}8(µ-I)4 was prepared by reacting GeI4 and Fe2(CO)9 in [BMIm]Cl/AlCl3 as ionic liquid (BMIm: 1-butyl-3-methylimidazolium). The cluster contains a Ge12Fe8 metal core consisting of a central Ge4 rectangle, two Ge2 pairs, and four single Ge atoms. These Ge units are interconnected by Fe atoms to a real Ge-Fe cluster. According to DFT calculations, Hund's localization criterion is fulfilled for the whole cluster if we assume three different atomic charges on the Ge4, Ge2, and Ge units.

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