Hybrid Disila-Crown Ethers as Hosts for Ammonium Cations: The O–Si–Si–O Linkage as an Acceptor for Hydrogen Bonding

Dankert, Fabian; Kirsten, R; Donsbach, Carsten; Hänisch, Carsten von

doi:10.3390/inorganics6010015

Cited by 13 publications

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“…Both effects are disadvantageous in terms of complex formation. , With the insertion of Si 2 Me 4 units rather than SiMe 2 units into a residual C 2 H 4 O framework (see Scheme b,c), we could demonstrate that these effects have to be taken into account but low basicity also originates from different architecture of cyclosiloxanes in comparison to crown ethers (Scheme a). Crown ethers bearing a single disilane unit readily form stable complexes with alkali and alkaline earth metal salts, and the coordination ability is comparable to that of the purely organic crown ethers which is confirmed by means of NMR experiments and DFT calculations. − Furthermore, even hydrogen bonding could be established as the incorporation of ammonium cations was realized . Very recently new insights into the Si–O bond were given as ligands bearing a single O–Si–Si–O linkage were found to be effective for the incorporation of exclusively hard cations.…”

Section: Introductionmentioning

confidence: 78%

Insights into the Coordination Ability of Siloxanes Employing Partially Silicon Based Crown Ethers: A Comparative Analysis of s-Block Metal Complexes

Dankert

Hänisch

2019

Inorg. Chem.

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Herein we present the synthesis and coordination chemistry of the partially silicon based crown ether analogues 1,2,4,5-tetrasila-benzo[15]crown-5 (1) and 1,2,4,5-tetrasila[18]crown-6 (7). Stable complexes of alkali and alkaline earth metal iodides could be obtained showing the good coordination ability of these ligands. The complexes [M A (1,2,4,5-tetrasila-benzo[15]crown-5)I] (M A = Li+ (2), Na+ (4)) and [M EA (1,2,4,5-tetrasila-benzo[15]crown-5)I2] (M EA = Mg2+ (3), Ca2+ (5), Sr2+ (6)) were obtained by equimolar reaction of 1 with the respective alkali or alkaline earth metal iodide. Depending on the ionic radii of the respective cations, the coordination modes of the siloxane backbone are significantly different and could be well-represented by means of 29Si NMR spectroscopy. In addition, we were able to generate the unusual dinuclear complex [Ba2(1,2,4,5-tetrasila[18]crown-6)2I4] (8) by reaction of 7 with BaI2. All compounds were characterized via single crystal X-ray diffraction (XRD) analysis.

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Section: Introductionmentioning

confidence: 78%

Insights into the Coordination Ability of Siloxanes Employing Partially Silicon Based Crown Ethers: A Comparative Analysis of s-Block Metal Complexes

Dankert

Hänisch

2019

Inorg. Chem.

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“…(d) , The [Ag(D 7 )] + cation was characterized as the salt of [SbF 6 ] − , and with [Ag(D 6 )][Al(OR F ) 4 ] and [Ag(D 6 )][AlF(OR F ) 3 ] (R F = C(CF 3 ) 3 ) there are also complexes of D 6 characterized. (e, f) − Binding modes of hybrid disila-crown ethers. Stable complexes of the alkali metal ions Li + , Na + , and K + , the alkaline earth metal cations Mg 2+ , Ca 2+ , Sr 2+ , and Ba 2+ , and the NH 4 + cation, as well as different anions including halides, could be isolated.…”

Section: Introductionmentioning

confidence: 99%

Not Non-Coordinating at All: Coordination Compounds of the Cyclodimethylsiloxanes D_n (D = Me₂SiO; n = 6, 7) and Group 2 Metal Cations

2019

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We present the coordination chemistry of the cyclodimethylsiloxanes D6 and D7 toward alkaline earth metal salts. The coordination chemistry of these macrocycles toward alkaline earth metals has been unprecedented to date, and we could show that these ligands coordinate better than previously thought. Direct reaction of alkaline earth metal salts with these ligands yields stable complexes even with a relatively strongly coordinating iodide anion. A handful of counterintuitive coordination compounds could be characterized by single-crystal X-ray diffraction analysis. Quantum chemical calculations of suited Born–Haber cycles showed that these complexes are indeed stable, for Mg2+ and Ca2+ even with iodide employed as the anion and for Sr2+ and Ba2+ in the presence of GaI3.

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“…The conversion of this disilene into the corresponding potassium disilenide and its reactivity towards various electrophiles are also described. Von Hänisch's group discusses the incorporation of a disilane unit into crown ether, leading the preparation of 1,2-disila [18]crown-6, as well as 1,2-disila-benzo [18]crown-6 [17]. The complexation ability with ammonium cations by these disilane-containing crown ethers is examined, and corresponding complexes are successfully isolated.…”

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confidence: 99%

Coordination Chemistry of Silicon

Inoue¹

2019

Inorganics

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It is with great pleasure to welcome readers to this Special Issue of Inorganics, devoted to "Coordination Chemistry of Silicon". Investigations into silicon compounds continue to afford a wealth of novel complexes, with unusual structures and brand-new reactivities. In fact, the ongoing quest for silicon complexes with novel properties has led to a large number of silicon compounds, that contain various types of ligands or substituents. Use of the divergent coordination behavior of silicon to construct sophisticated low-and hyper-valent silicon complexes makes it possible to change their electronic structures and properties. Therefore, progress of the coordination chemistry of silicon can be the key concept for the design and development of next generation silicon compound-based applications. This Special Issue is associated with the most recent advances in coordination chemistry of silicon with transition metals, as well as main group elements, including the stabilization of low-valent silicon species through the coordination of electron-donor ligands, such as N-heterocyclic carbenes (NHCs) and their derivatives [1,2]. This Special Issue is also dedicated to the development of novel synthetic methodologies, structural elucidations, bonding analyses, and possible applications in catalysis or chemical transformations, using related organosilicon compounds [3]. Besides, recent years have witnessed great research efforts in silicon-based polymer chemistry, as well as silicon surface chemistry, which have become increasingly important for unveiling the correlations between nanoscopic structural features and macroscopic material properties, including the coordination behavior at silicon.The 19 articles composing this Special Issue can be considered as a representative selection of the current research on this topic, reflecting the diversity of silicon chemistry and yield an impressive compilation.Intrinsic coordination behaviors of silanes towards transition metals are the subject of several articles in this issue. For example, Nakata et al. discuss the synthesis and structure of a hydrido platinum(II) complex with a dihydrosilyl ligand that bears a bulky 9-triptycyl group [4]. The ligand exchange reaction of this mononuclear (hydrido)(dihydrosilyl) complex with various phosphines has also been studied. Sunada and coworkers provide an elegant method for accessing planar tetrapalladium clusters starting from octa(isopropyl)cyclotetrasilane through the insertion of palladium atoms into the Si-Si bonds of the cyclotetrasilane [5]. While the ligand exchange reaction with NHCs yields the more coordinatively unsaturated cluster, reaction with a trimethylolpropane phosphite affords a planar tripalladium cluster. Wagler and coworkers demonstrate a striking coordination chemistry of (2-pyridyloxy)silanes with transition metals (Pd, Cu) [6]. The molecular structures of the complexes have been elucidated by crystallographic analysis, and further computational investigations provided an in-depth understanding of the interatomic ...

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Hybrid Disila-Crown Ethers as Hosts for Ammonium Cations: The O–Si–Si–O Linkage as an Acceptor for Hydrogen Bonding

Cited by 13 publications

References 50 publications

Insights into the Coordination Ability of Siloxanes Employing Partially Silicon Based Crown Ethers: A Comparative Analysis of s-Block Metal Complexes

Insights into the Coordination Ability of Siloxanes Employing Partially Silicon Based Crown Ethers: A Comparative Analysis of s-Block Metal Complexes

Not Non-Coordinating at All: Coordination Compounds of the Cyclodimethylsiloxanes D_n (D = Me₂SiO; n = 6, 7) and Group 2 Metal Cations

Coordination Chemistry of Silicon

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Hybrid Disila-Crown Ethers as Hosts for Ammonium Cations: The O–Si–Si–O Linkage as an Acceptor for Hydrogen Bonding

Cited by 13 publications

References 50 publications

Insights into the Coordination Ability of Siloxanes Employing Partially Silicon Based Crown Ethers: A Comparative Analysis of s-Block Metal Complexes

Insights into the Coordination Ability of Siloxanes Employing Partially Silicon Based Crown Ethers: A Comparative Analysis of s-Block Metal Complexes

Not Non-Coordinating at All: Coordination Compounds of the Cyclodimethylsiloxanes Dn (D = Me2SiO; n = 6, 7) and Group 2 Metal Cations

Coordination Chemistry of Silicon

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Not Non-Coordinating at All: Coordination Compounds of the Cyclodimethylsiloxanes D_n (D = Me₂SiO; n = 6, 7) and Group 2 Metal Cations