Pub Date : 2015-07-03DOI: 10.3390/INORGANICS3030309
P. Hermosilla‐Ibáñez, K. Muñoz-Becerra, V. Paredes-García, E. L. Fur, E. Spodine, D. Venegas‐Yazigi
This review summarizes all published data until April 2015 related to crystalline lattices formed by the [V12B18O60] core, which generates polyanionic clusters with different degrees of protonation and mixed-valence ratios. The negative charge of this cluster is counterbalanced by different cations such as protonated amines, hydronium, and alkaline, and transition metal ions. The cluster is shown to form extended 1D, 2D, or 3D frameworks by forming covalent bonds or presenting hydrogen bond interactions with the present secondary cations. These cations have little influence on the solid state reflectance UV-visible spectra of the polyanionic cluster, but are shown to modify the FT-IR spectra and the magnetic behavior of the different reported species.
{"title":"Structural and Electronic Properties of Polyoxovanadoborates Containing the [V12B18O60] Core in Different Mixed Valence States","authors":"P. Hermosilla‐Ibáñez, K. Muñoz-Becerra, V. Paredes-García, E. L. Fur, E. Spodine, D. Venegas‐Yazigi","doi":"10.3390/INORGANICS3030309","DOIUrl":"https://doi.org/10.3390/INORGANICS3030309","url":null,"abstract":"This review summarizes all published data until April 2015 related to crystalline lattices formed by the [V12B18O60] core, which generates polyanionic clusters with different degrees of protonation and mixed-valence ratios. The negative charge of this cluster is counterbalanced by different cations such as protonated amines, hydronium, and alkaline, and transition metal ions. The cluster is shown to form extended 1D, 2D, or 3D frameworks by forming covalent bonds or presenting hydrogen bond interactions with the present secondary cations. These cations have little influence on the solid state reflectance UV-visible spectra of the polyanionic cluster, but are shown to modify the FT-IR spectra and the magnetic behavior of the different reported species.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2015-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82984833","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2015-05-20DOI: 10.3390/INORGANICS3020178
D. M. Fernandes, M. Nunes, R. Carvalho, R. Bacsa, I. Mbomekallé, P. Serp, P. Oliveira, C. Freire
A novel hybrid nanocomposite, PMo11V@N-doped few layer graphene, was prepared by a one-step protocol through direct immobilization of the tetrabutylammonium salt of a vanadium-substituted phosphomolybdate (PMo11V) onto N-doped few layer graphene (N-FLG). The nanocomposite characterization by FTIR and XPS confirmed its successful synthesis. Glassy carbon modified electrodes with PMo11V and PMo11V@N-FLG showed cyclic voltammograms consistent with surface-confined redox processes attributed to Mo-centred reductions (MoVI→MoV) and a vanadium reduction (VV→VIV). Furthermore, PMo11V@N-FLG modified electrodes showed good stability and well-resolved redox peaks with high current intensities. The observed enhancement of PMo11V electrochemical properties is a consequence of a strong electronic communication between the POM and the N-doped few layer graphene. Additionally, the electro-catalytic and sensing properties towards acetaminophen (AC) and theophylline (TP) were evaluated by voltammetric techniques using a glassy carbon electrode modified with PMo11V@N-FLG. Under the conditions used, the square wave voltammetric peak current increased linearly with AC concentration in the presence of TP, but showing two linear ranges: 1.2 × 10−6 to 1.2 × 10−4 and 1.2 × 10−4 to 4.8 × 10−4 mol dm−3, with different AC sensitivity values, 0.022 A/mol dm−3 and 0.035 A/mol dm−3, respectively (detection limit, DL = 7.5 × 10−7 mol dm−3).
{"title":"Biomolecules Electrochemical Sensing Properties of a PMo11V@N-Doped Few Layer Graphene Nanocomposite","authors":"D. M. Fernandes, M. Nunes, R. Carvalho, R. Bacsa, I. Mbomekallé, P. Serp, P. Oliveira, C. Freire","doi":"10.3390/INORGANICS3020178","DOIUrl":"https://doi.org/10.3390/INORGANICS3020178","url":null,"abstract":"A novel hybrid nanocomposite, PMo11V@N-doped few layer graphene, was prepared by a one-step protocol through direct immobilization of the tetrabutylammonium salt of a vanadium-substituted phosphomolybdate (PMo11V) onto N-doped few layer graphene (N-FLG). The nanocomposite characterization by FTIR and XPS confirmed its successful synthesis. Glassy carbon modified electrodes with PMo11V and PMo11V@N-FLG showed cyclic voltammograms consistent with surface-confined redox processes attributed to Mo-centred reductions (MoVI→MoV) and a vanadium reduction (VV→VIV). Furthermore, PMo11V@N-FLG modified electrodes showed good stability and well-resolved redox peaks with high current intensities. The observed enhancement of PMo11V electrochemical properties is a consequence of a strong electronic communication between the POM and the N-doped few layer graphene. Additionally, the electro-catalytic and sensing properties towards acetaminophen (AC) and theophylline (TP) were evaluated by voltammetric techniques using a glassy carbon electrode modified with PMo11V@N-FLG. Under the conditions used, the square wave voltammetric peak current increased linearly with AC concentration in the presence of TP, but showing two linear ranges: 1.2 × 10−6 to 1.2 × 10−4 and 1.2 × 10−4 to 4.8 × 10−4 mol dm−3, with different AC sensitivity values, 0.022 A/mol dm−3 and 0.035 A/mol dm−3, respectively (detection limit, DL = 7.5 × 10−7 mol dm−3).","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2015-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87044959","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2015-05-13DOI: 10.3390/INORGANICS3020118
A. Klein, M. Neugebauer, Alexander Krest, A. Lüning, Simon Garbe, N. Arefyeva, N. Schlörer
The five coordinate organoplatinum complex [Pt(bpy)(cod)(Me)][SbF6] (cod = 1,5-cyclooctadiene, bpy = 2,2’-bipyridine) was obtained reacting [Pt(cod)(Me)Cl] with Ag[SbF6] and bpy and characterized by multiple spectroscopy (IR and NMR) and single crystal XRD. Although the application of the τ values for the discrimination between trigonal bipyramidal vs. square pyramidal coordination fails, the molecular structure can be unequivocally described as basally-distorted trigonal bipyramidal. Detailed multinuclear NMR spectroscopy in solution at ambient temperature gives strong evidence for the same structure; corresponding low-temperature measurements down to −70 °C revealed no marked dynamic processes.
{"title":"Five Coordinate Platinum(II) in [Pt(bpy)(cod)(Me)][SbF6]: A Structural and Spectroscopic Study","authors":"A. Klein, M. Neugebauer, Alexander Krest, A. Lüning, Simon Garbe, N. Arefyeva, N. Schlörer","doi":"10.3390/INORGANICS3020118","DOIUrl":"https://doi.org/10.3390/INORGANICS3020118","url":null,"abstract":"The five coordinate organoplatinum complex [Pt(bpy)(cod)(Me)][SbF6] (cod = 1,5-cyclooctadiene, bpy = 2,2’-bipyridine) was obtained reacting [Pt(cod)(Me)Cl] with Ag[SbF6] and bpy and characterized by multiple spectroscopy (IR and NMR) and single crystal XRD. Although the application of the τ values for the discrimination between trigonal bipyramidal vs. square pyramidal coordination fails, the molecular structure can be unequivocally described as basally-distorted trigonal bipyramidal. Detailed multinuclear NMR spectroscopy in solution at ambient temperature gives strong evidence for the same structure; corresponding low-temperature measurements down to −70 °C revealed no marked dynamic processes.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2015-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86434729","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2015-02-03DOI: 10.3390/inorganics3010021
W. Casey, M. Olmstead, Caitlyn R. Hazlett, Chelsey Lamar, T. Forbes
A new 30-center Ga(III)-oxy-hydroxide cation cluster was synthesized by hydrolysis of an aqueous GaCl3 solution near pH = 2.5 and crystallized using 2,6-napthalene disulfonate (NDS). The cluster has 30 metal centers and a nominal stoichiometry: [Ga30(μ4-O)12(μ3-O)4(μ3-OH)4(μ2-OH)42(H2O)16](2,6-NDS)6, where 2,6-NDS = 2,6-napthalene disulfonate This cluster augments the very small library of Group 13 clusters that have been isolated from aqueous solution and closely resembles one other Ga(III) cluster with 32 metal centers that had been isolated using curcurbit ligands. These clusters have uncommon linked Ga(O)4 centers and sets of both protonated and unprotonated μ3-oxo.
{"title":"A New Nanometer-Sized Ga(III)-Oxyhydroxide Cation","authors":"W. Casey, M. Olmstead, Caitlyn R. Hazlett, Chelsey Lamar, T. Forbes","doi":"10.3390/inorganics3010021","DOIUrl":"https://doi.org/10.3390/inorganics3010021","url":null,"abstract":"A new 30-center Ga(III)-oxy-hydroxide cation cluster was synthesized by hydrolysis of an aqueous GaCl3 solution near pH = 2.5 and crystallized using 2,6-napthalene disulfonate (NDS). The cluster has 30 metal centers and a nominal stoichiometry: [Ga30(μ4-O)12(μ3-O)4(μ3-OH)4(μ2-OH)42(H2O)16](2,6-NDS)6, where 2,6-NDS = 2,6-napthalene disulfonate This cluster augments the very small library of Group 13 clusters that have been isolated from aqueous solution and closely resembles one other Ga(III) cluster with 32 metal centers that had been isolated using curcurbit ligands. These clusters have uncommon linked Ga(O)4 centers and sets of both protonated and unprotonated μ3-oxo.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2015-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83415909","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2014-12-10DOI: 10.3390/INORGANICS2040660
Yoshida Takuya, Yuta Yasuda, Eri Nagashima, Hidekazu Arai, Satoshi Matsunaga, K. Nomiya
Novel phosphanegold(I) cluster cations combined with polyoxometalate (POM) anions, i.e., intercluster compounds, [(Au{P(m-FPh)3})4(μ4-O)]2[{(Au{P(m-FPh)3})2 (μ-OH)}2][α-PMo12O40]2·EtOH (1), [(Au{P(m-FPh)3})4(μ4-O)]2[α-SiMo12O40]·4H2O (2), [(Au{P(m-MePh)3})4(μ4-O)]2[α-SiM12O40] (M = W (3), Mo (4)) and [{(Au {P(p-MePh)3})4(μ4-O)}{(Au{P(p-MePh)3})3(μ3-O)}][α-PW12O40] (5) were synthesized by POM-mediated clusterization, and unequivocally characterized by elemental analysis, TG/DTA, FT-IR, X-ray crystallography, solid-state CPMAS 31P NMR and solution (1H, 31P{1H}) NMR. Formation of the these gold(I) cluster cations was strongly dependent upon the charge density and acidity of the POMs, and the substituents and substituted positions on the aryl group of triarylphosphane ligands. These gold(I) cluster cations contained various bridged-oxygen atoms such as μ4-O, μ3-O and μ-OH groups.
{"title":"Various Oxygen-Centered Phosphanegold(I) Cluster Cations Formed by Polyoxometalate (POM)-Mediated Clusterization: Effects of POMs and Phosphanes","authors":"Yoshida Takuya, Yuta Yasuda, Eri Nagashima, Hidekazu Arai, Satoshi Matsunaga, K. Nomiya","doi":"10.3390/INORGANICS2040660","DOIUrl":"https://doi.org/10.3390/INORGANICS2040660","url":null,"abstract":"Novel phosphanegold(I) cluster cations combined with polyoxometalate (POM) anions, i.e., intercluster compounds, [(Au{P(m-FPh)3})4(μ4-O)]2[{(Au{P(m-FPh)3})2 (μ-OH)}2][α-PMo12O40]2·EtOH (1), [(Au{P(m-FPh)3})4(μ4-O)]2[α-SiMo12O40]·4H2O (2), [(Au{P(m-MePh)3})4(μ4-O)]2[α-SiM12O40] (M = W (3), Mo (4)) and [{(Au {P(p-MePh)3})4(μ4-O)}{(Au{P(p-MePh)3})3(μ3-O)}][α-PW12O40] (5) were synthesized by POM-mediated clusterization, and unequivocally characterized by elemental analysis, TG/DTA, FT-IR, X-ray crystallography, solid-state CPMAS 31P NMR and solution (1H, 31P{1H}) NMR. Formation of the these gold(I) cluster cations was strongly dependent upon the charge density and acidity of the POMs, and the substituents and substituted positions on the aryl group of triarylphosphane ligands. These gold(I) cluster cations contained various bridged-oxygen atoms such as μ4-O, μ3-O and μ-OH groups.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2014-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79133805","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2014-11-06DOI: 10.3390/INORGANICS2040606
W. Lojkowski, C. Leonelli, T. Chudoba, J. Wojnarowicz, A. Majcher, A. Mazurkiewicz
Microwave Solvothermal Synthesis (MSS) is a chemical technology, where apart from possible effects of microwaves on the chemical reaction paths, microwave heating allows the precise planning of a time-temperature schedule, as well as to achieve high super-saturation of the reagents uniformly in the reactor vessel. Thus, MSS is suitable for production of nanoparticles with small grain size distribution and a high degree of crystallinity. A further advantage of the technology is a much lower synthesis temperature than for gas phase, plasma or sol-gel technologies. New reactors have been developed to exploit these advantages of the MSS technology of nanoparticles synthesis and to scale up the production rate. Reactor design and realization has been shown to be decisive and critical for the control of the MSS technology. Examples of oxidic and phosphatic nanoparticles synthesis have been reported.
{"title":"High-Energy-Low-Temperature Technologies for the Synthesis of Nanoparticles: Microwaves and High Pressure","authors":"W. Lojkowski, C. Leonelli, T. Chudoba, J. Wojnarowicz, A. Majcher, A. Mazurkiewicz","doi":"10.3390/INORGANICS2040606","DOIUrl":"https://doi.org/10.3390/INORGANICS2040606","url":null,"abstract":"Microwave Solvothermal Synthesis (MSS) is a chemical technology, where apart from possible effects of microwaves on the chemical reaction paths, microwave heating allows the precise planning of a time-temperature schedule, as well as to achieve high super-saturation of the reagents uniformly in the reactor vessel. Thus, MSS is suitable for production of nanoparticles with small grain size distribution and a high degree of crystallinity. A further advantage of the technology is a much lower synthesis temperature than for gas phase, plasma or sol-gel technologies. New reactors have been developed to exploit these advantages of the MSS technology of nanoparticles synthesis and to scale up the production rate. Reactor design and realization has been shown to be decisive and critical for the control of the MSS technology. Examples of oxidic and phosphatic nanoparticles synthesis have been reported.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2014-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"72716145","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2014-06-13DOI: 10.3390/INORGANICS2020313
Fang Xu, N. Wang, Hong Chang, Yongde Xia, Yanqiu Zhu
This manuscript demonstrates the design, modification and initial investigation of a rotary furnace for the manufacturing of inorganic fullerene WS2 nanoparticles. Different preparation methods starting with various precursors have been investigated, of which the gas-solid reaction starting with WO3 nanoparticles was the most efficient technique. Furthermore, the influence of temperature, reaction time, and reaction gases etc. on the synthesis of inorganic fullerene WS2 nanomaterials was investigated, and these parameters were optimised based on combined characterisations using XRD, SEM and TEM. In addition, the furnace was further modified to include a baffled tube, a continuous gas-blow feeding system, and a collection system, in order to improve the batch yield and realise continuous production. This technique has improved the production from less than 1 g/batch in a traditional tube furnace to a few tens of g/batch, and could be easily scaled up to industry level production.
{"title":"Continuous Production of IF-WS2 Nanoparticles by a Rotary Process","authors":"Fang Xu, N. Wang, Hong Chang, Yongde Xia, Yanqiu Zhu","doi":"10.3390/INORGANICS2020313","DOIUrl":"https://doi.org/10.3390/INORGANICS2020313","url":null,"abstract":"This manuscript demonstrates the design, modification and initial investigation of a rotary furnace for the manufacturing of inorganic fullerene WS2 nanoparticles. Different preparation methods starting with various precursors have been investigated, of which the gas-solid reaction starting with WO3 nanoparticles was the most efficient technique. Furthermore, the influence of temperature, reaction time, and reaction gases etc. on the synthesis of inorganic fullerene WS2 nanomaterials was investigated, and these parameters were optimised based on combined characterisations using XRD, SEM and TEM. In addition, the furnace was further modified to include a baffled tube, a continuous gas-blow feeding system, and a collection system, in order to improve the batch yield and realise continuous production. This technique has improved the production from less than 1 g/batch in a traditional tube furnace to a few tens of g/batch, and could be easily scaled up to industry level production.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2014-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84753516","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2014-04-29DOI: 10.3390/INORGANICS2020177
V. Brüser, R. Popovitz‐Biro, A. Albu‐Yaron, T. Lorenz, G. Seifert, R. Tenne, A. Zak
The synthesis of inorganic nanotubes (INT) from layered compounds of a small size (<10 nm in diameter) and number of layers (<4) is not a trivial task. Calculations based on density functional tight-binding theory (DFTB) predict that under highly exergonic conditions, the reaction could be driven into a “window” of (meta-) stability, where 1–3-layer nanotubes will be formed. Indeed, in this study, single- to triple-wall WS2 nanotubes with a diameter of 3–7 nm and a length of 20–100 nm were produced by high-power plasma irradiation of multiwall WS2 nanotubes. As target materials, plane crystals (2H), quasi spherical nanoparticles (IF) and multiwall, 20–30 layers, WS2 nanotubes were assessed. Surprisingly, only INT-WS2 treated by plasma resulted in very small, and of a few layers, “daughter” nanotubules. The daughter nanotubes occur mostly attached to the outer surface of the predecessor, i.e., the multiwall “mother” nanotubes. They appear having either a common growth axis with the multiwall nanotube or tilted by approximately 30° or 60° with respect to its axis. This suggests that the daughter nanotubes are generated by exfoliation along specific crystallographic directions. A growth mechanism for the daughter nanotubes is proposed. High resolution transmission and scanning electron microscopy (HRTEM/HRSEM) analyses revealed the distinctive nanoscale structures and helped elucidating their growth mechanism.
{"title":"Single- to Triple-Wall WS2 Nanotubes Obtained by High-Power Plasma Ablation of WS2 Multiwall Nanotubes","authors":"V. Brüser, R. Popovitz‐Biro, A. Albu‐Yaron, T. Lorenz, G. Seifert, R. Tenne, A. Zak","doi":"10.3390/INORGANICS2020177","DOIUrl":"https://doi.org/10.3390/INORGANICS2020177","url":null,"abstract":"The synthesis of inorganic nanotubes (INT) from layered compounds of a small size (<10 nm in diameter) and number of layers (<4) is not a trivial task. Calculations based on density functional tight-binding theory (DFTB) predict that under highly exergonic conditions, the reaction could be driven into a “window” of (meta-) stability, where 1–3-layer nanotubes will be formed. Indeed, in this study, single- to triple-wall WS2 nanotubes with a diameter of 3–7 nm and a length of 20–100 nm were produced by high-power plasma irradiation of multiwall WS2 nanotubes. As target materials, plane crystals (2H), quasi spherical nanoparticles (IF) and multiwall, 20–30 layers, WS2 nanotubes were assessed. Surprisingly, only INT-WS2 treated by plasma resulted in very small, and of a few layers, “daughter” nanotubules. The daughter nanotubes occur mostly attached to the outer surface of the predecessor, i.e., the multiwall “mother” nanotubes. They appear having either a common growth axis with the multiwall nanotube or tilted by approximately 30° or 60° with respect to its axis. This suggests that the daughter nanotubes are generated by exfoliation along specific crystallographic directions. A growth mechanism for the daughter nanotubes is proposed. High resolution transmission and scanning electron microscopy (HRTEM/HRSEM) analyses revealed the distinctive nanoscale structures and helped elucidating their growth mechanism.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2014-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77431687","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2013-12-12DOI: 10.3390/INORGANICS1010046
G. Marshall, Ashley J. Wooles, D. P. Mills, W. Lewis, A. Blake, S. Liddle
We report the extension of the series of {BIPMTMSH}− (BIPMR = C{PPh2NR}2, TMS = trimethylsilyl) derived rare earth methanides by the preparation of [Ln(BIPMTMSH)(I)2(THF)] (Ln = Nd, Gd, Tb), 1a–c, in 34–50% crystalline yields via the reaction of [Ln(I)3(THF)3.5] with [Cs(BIPMTMSH)]. Similarly, we have extended the range of {BIPMMesH}− (Mes = 2,4,6-trimethylphenyl) derived rare earth methanides with the preparation of [Gd(BIPMMesH)(I)2(THF)2], 3, (49%) and [Yb(BIPMMesH)(I)2(THF)], 4, (26%), via the reaction of [Ln(I)3(THF)3.5] with [{K(BIPMMesH)}2]. Attempts to prepare dysprosium and erbium analogues of 3 or 4 were not successful, with the ion pair species [Ln(BIPMMesH)2][BIPMMesH] (Ln = Dy, Er), 5a–b, isolated in 31–39% yield. The TMEDA (N',N',N",N"-tetramethylethylenediamine) adducts [Ln(BIPMMesH)(I)2(TMEDA)] (Ln = La, Gd), 6a–b, were prepared in quantitative yield via the dissolution of [La(BIPMMesH)(I)2(THF)] or 3 in a TMEDA/THF solution. The reactions of [Ln(BIPMMesH)(I)2(THF)] [Ln = La, Ce, Pr, and Gd (3)] or 6a–b with a selection of bases did not afford [La(BIPMMes)(I)(S)n] (S = solvent) as predicted, but instead led to the isolation of the heteroleptic complexes [Ln(BIPMMes)(BIPMMesH)] (Ln = La, Ce, Pr and Gd), 7a–d, in low yields due to ligand scrambling.
{"title":"Synthesis and Characterisation of Lanthanide N-Trimethylsilyl and -Mesityl Functionalised Bis(iminophosphorano)methanides and -Methanediides","authors":"G. Marshall, Ashley J. Wooles, D. P. Mills, W. Lewis, A. Blake, S. Liddle","doi":"10.3390/INORGANICS1010046","DOIUrl":"https://doi.org/10.3390/INORGANICS1010046","url":null,"abstract":"We report the extension of the series of {BIPMTMSH}− (BIPMR = C{PPh2NR}2, TMS = trimethylsilyl) derived rare earth methanides by the preparation of [Ln(BIPMTMSH)(I)2(THF)] (Ln = Nd, Gd, Tb), 1a–c, in 34–50% crystalline yields via the reaction of [Ln(I)3(THF)3.5] with [Cs(BIPMTMSH)]. Similarly, we have extended the range of {BIPMMesH}− (Mes = 2,4,6-trimethylphenyl) derived rare earth methanides with the preparation of [Gd(BIPMMesH)(I)2(THF)2], 3, (49%) and [Yb(BIPMMesH)(I)2(THF)], 4, (26%), via the reaction of [Ln(I)3(THF)3.5] with [{K(BIPMMesH)}2]. Attempts to prepare dysprosium and erbium analogues of 3 or 4 were not successful, with the ion pair species [Ln(BIPMMesH)2][BIPMMesH] (Ln = Dy, Er), 5a–b, isolated in 31–39% yield. The TMEDA (N',N',N\",N\"-tetramethylethylenediamine) adducts [Ln(BIPMMesH)(I)2(TMEDA)] (Ln = La, Gd), 6a–b, were prepared in quantitative yield via the dissolution of [La(BIPMMesH)(I)2(THF)] or 3 in a TMEDA/THF solution. The reactions of [Ln(BIPMMesH)(I)2(THF)] [Ln = La, Ce, Pr, and Gd (3)] or 6a–b with a selection of bases did not afford [La(BIPMMes)(I)(S)n] (S = solvent) as predicted, but instead led to the isolation of the heteroleptic complexes [Ln(BIPMMes)(BIPMMesH)] (Ln = La, Ce, Pr and Gd), 7a–d, in low yields due to ligand scrambling.","PeriodicalId":13580,"journal":{"name":"Inorganics (Basel)","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2013-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84439630","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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