Solvent influences on the molecular aggregation of magnesium aryloxides: synthesis, crystal structure, and solution characterization of Mg(OAr)2(L)3 (OAr=DMP, DIP, TCP) and [Mg(DIP)2]3

Zechmann, Cecilia A.; Boyle, Timothy J.; Rodriguez, Mark A.; Kemp, Richard A.

doi:10.1016/s0277-5387(00)00566-0

Cited by 30 publications

(22 citation statements)

References 12 publications

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“…The base thf adds to (RO)Mg(BH 4 ) compounds in ratios 1 : 1 (18, 19, 20, 25 [26], (Mg(O-Tol)(thf) 2 [27], [(2,6-iPr 2 C 6 H 3 O) 2 Mg] 3 [28] or Mg(OC 6 H 3 -(2,6-Me 2 )(py) 3 [28]. Coordination numbers 3, 4, and 5 are realized in these compounds.…”

Section: Discussionmentioning

confidence: 99%

Metal Tetrahydroborates and Tetrahydroborato Metalates. 30 [1] Solvates of Alcoholato‐, Phenolato‐, and Bis(trimethylsilyl)amido‐Magnesium Tetrahydroborates XMgBH₄(L_n). Metall Tetrahydroborate und Tetrahydroborato Metallate, 30 [1]. Solvate der Alkoholato‐, Phenolato‐ und Bis(trimethylsilyl)amino‐magnesium‐tetrahydroborate XMgBH₄(L_n)

Bremer¹,

Linti²,

Nöth³

et al. 2005

Zeitschrift anorg allge chemie

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Section: Discussionmentioning

confidence: 99%

Metal Tetrahydroborates and Tetrahydroborato Metalates. 30 [1] Solvates of Alcoholato‐, Phenolato‐, and Bis(trimethylsilyl)amido‐Magnesium Tetrahydroborates XMgBH₄(L_n). Metall Tetrahydroborate und Tetrahydroborato Metallate, 30 [1]. Solvate der Alkoholato‐, Phenolato‐ und Bis(trimethylsilyl)amino‐magnesium‐tetrahydroborate XMgBH₄(L_n)

Bremer¹,

Linti²,

Nöth³

et al. 2005

Zeitschrift anorg allge chemie

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“…Trinuclear homoleptic Mg compounds displaying two different ligand environments in a 1:2 ratio for the terminal and bridging positions are more common. [62][63][64][65] Trinuclear divalent lanthanide complexes of composition Ln{[m-N(SiHMe 2 ) 2 ] 2 Ln[N(SiHMe 2 ) 2 ](thf)} 2 (Ln = Sm, [66] Yb, [67] and Eu [68] ) have been also described. As in the case of complex 4, the coordinatively unsaturated and electron-deficient Ln(II) )] with an excess of 4 in pentane over a period of 2 days, followed by extraction with a 1:3 toluene/pentane mixture, provided 5 in 37 % yield (Scheme 5).…”

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confidence: 99%

Highly Fluorinated Tris(indazolyl)borate Silylamido Complexes of the Heavier Alkaline Earth Metals: Synthesis, Characterization, and Efficient Catalytic Intramolecular Hydroamination

Romero

Roşca

Sarazin

et al. 2015

Chemistry A European J

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Heteroleptic silylamido complexes of the heavier alkaline earth elements calcium and strontium containing the highly fluorinated 3-phenyl hydrotris(indazolyl)borate {F12-Tp(4Bo, 3Ph)}(-) ligand have been synthesized by using salt metathesis reactions. The homoleptic precursors [Ae{N(SiMe3)2}2] (Ae = Ca, Sr) were treated with [Tl(F12-Tp(4Bo, 3Ph))] in pentane to form the corresponding heteroleptic complexes [(F12-Tp(4Bo, 3Ph))Ae{N(SiMe3)2}] (Ae = Ca (1); Sr (3)). Compounds 1 and 3 are inert towards intermolecular redistribution. The molecular structures of 1 and 3 have been determined by using X-ray diffraction. Compound 3 exhibits a Sr⋅⋅⋅MeSi agostic distortion. The synthesis of the homoleptic THF-free compound [Ca{N(SiMe2H)2}2] (4) by transamination reaction between [Ca{N(SiMe3)2}2] and HN(SiMe2H)2 is also reported. This precursor constitutes a convenient starting material for the subsequent preparation of the THF-free complex [(F12-Tp(4Bo, 3Ph))Ca{N(SiMe2H)2}] (5). Compound 5 is stabilized in the solid state by a Ca⋅⋅⋅β-Si-H agostic interaction. Complexes 1 and 3 have been used as precatalysts for the intramolecular hydroamination of 2,2-dimethylpent-4-en-1-amine. Compound 1 is highly active, converting completely 200 equivalents of aminoalkene in 16 min with 0.50 mol % catalyst loading at 25 °C.

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“…Zechmann et al reported that solutions of several magnesium alkoxides of the same stoichiometry can have variable speciation: dissolved complexes are not necessarily well represented by structural characterizations of the solid state. 21,22 They also noted that magnesium alkoxides and aryloxides have limited solubility, even in donor solvents, because of their tendency to form oligomeric structures; 22 aluminum alkoxides and aluminum alkoxide chlorides are significantly more soluble in organic solvents than are the corresponding magnesium alkoxides. 23,24 The solutions of aryloxide:AlCl 3 ensemble, prepared using either Bu 2 Mg or magnesium metal, are electrochemically comparable in terms of deposition overpotential to those reported by Nelson et al 13 (see Table I).…”

Section: Resultsmentioning

confidence: 99%

Structural Effects of Magnesium Dialkoxides as Precursors for Magnesium-Ion Electrolytes

Herb

Nist-Lund

Schwartz

et al. 2015

ECS Electrochemistry Letters

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A challenge for magnesium ion battery research is the development of electrolytes that are capable of reversible magnesium electrodeposition through multiple cycles. Magnesium alkoxide chlorides and aryloxide chlorides are known magnesium ion electrolytes when used in conjunction with aluminum chloride. Herein we report the effects of structural variation in several dialkoxy and diaryloxy magnesium complex aggregates with aluminum chloride, Mg(OR) 2 :AlCl 3 (R = iPr, t-Bu, phenyl), on electrochemical characteristics of their solutions and on compositions of the magnesium-containing deposits they yield. We also report the synthesis of a magnesium phenoxide-based electrolyte directly from magnesium metal. © The Author Nonaqueous magnesium ion batteries that use a metallic magnesium anode are attractive due to their high theoretical volumetric energy density and comparatively low cost of materials compared to lithium ion systems.1,2 Studies incorporating Grignard-based electrolytes for magnesium electrodeposition date back to the early twentieth century, 3 but their use as electrolytes for magnesium batteries became of interest only as recently as 1990.4 Aurbach et al. 5 studied electrolyte solutions that were synthesized by reacting an alkylmagnesium halide or a dialkylmagnesium species with a Lewis acid of general structure R x AlCl 3-x . The complex species that result are capable of reversible magnesium electrodeposition, yet Barile et al. showed that these types of adducts decompose as a function of cycle count, based on NMR and GC-MS of the electrolyte and on SEM-EDS analysis of the electrodeposited metal.6 As such, the development of other, more suitable electrolytes for reversible magnesium electrodeposition is paramount. Most studies focus on modifying the Lewis acid component of the electrolyte mixture, either by modifying the anion 7 or the metal center; 8-10 in contrast, we focus on the magnesium species.It is known that phenoxymagnesium chloride 11 and alkoxymagnesium chloride 12 solutions react with aluminum chloride to generate electrolytes with good deposition overpotentials and acceptable conductivity. Nelson et al. studied phenol-based systems by modifying substituents on the aromatic ring; electron-withdrawing substituents showed higher oxidative stability of ca. 0.4 V more positive than the parent phenol.13 Magnesium alkoxides have also been employed as additives for magnesium electrolyte systems, 14 as have thiols 15 and amides. [16][17][18] For example, Zhao-Karger et al. found that magnesium bisamide compounds in combination with aluminum chloride showed comparable electrochemical performance in a variety of ethereal solvents to species derived from Grignard reagents, yet were easier to handle. 18 Here we report that magnesium dialkoxides and diaryloxidebased electrolyte solutions can be used for reversible magnesium electrodeposition whose properties are a function of ligand structure; we also show that an active complex can be prepared directly from magnesium metal. ExperimentalDi-n-butylma...

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Solvent influences on the molecular aggregation of magnesium aryloxides: synthesis, crystal structure, and solution characterization of Mg(OAr)2(L)3 (OAr=DMP, DIP, TCP) and [Mg(DIP)2]3

Cited by 30 publications

References 12 publications

Highly Fluorinated Tris(indazolyl)borate Silylamido Complexes of the Heavier Alkaline Earth Metals: Synthesis, Characterization, and Efficient Catalytic Intramolecular Hydroamination

Structural Effects of Magnesium Dialkoxides as Precursors for Magnesium-Ion Electrolytes

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