s-Block Organometallics: Analysis of Ion-Association and Noncovalent Interactions on Structure and Function in Benzyl-Based Compounds

Torvisco, Ana; Ruhlandt‐Senge, Karin

doi:10.1021/ic201148d

Cited by 51 publications

(40 citation statements)

References 153 publications

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“…Furthermore, this ligand binds both through the pyrazolyl bases and through the α‐carbon atom (κ 2 N ,κ C coordination mode). Calcium‐bound carbon atoms often show characteristic low‐field shifts in their 13 C{ 1 H} NMR spectra, as also observed for, e.g., phenylcalcium and benzylcalcium complexes …”

Section: Propertiesmentioning

confidence: 53%

s‐Block Metal Complexes with Bis‐ and Tris(pyrazolyl)methane and ‐methanide Ligands

et al. 2016

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Substituted bis-and tris(pyrazolyl)methanes and -methanides are isoelectronic with the corresponding pyrazolylsubstituted boranates, but the use of these Lewis bases in the coordination chemistry of the s-block metals has attracted attention only quite recently. Many lithium and magnesium complexes have been isolated and characterized, but for the heavier alkali and alkaline earth metals much less information is available. Beryllium complexes are unknown, due to the toxicity of this lightest alkaline earth metal. The bis-and tris(pyrazolyl)methanes and -methanides act as multidentate ligands to the metal ions and commonly bind through the pyrazolyl bases. Content

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Section: Propertiesmentioning

confidence: 53%

s‐Block Metal Complexes with Bis‐ and Tris(pyrazolyl)methane and ‐methanide Ligands

et al. 2016

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“…While, for decades, this chemistry was mainly focused on cyclic π-perimeter hydrocarbons like cyclopentadienide anions, [41] recent years have seen exciting developments in the field of aryl, [42] allyl, [43] and benzyl derivatives. [44] We, and others working in groups have been engaged in determining the structure and reactivity of alkaline earth metal species with reference to the design and development of efficient catalysts. [39,45] The heavier alkaline earth metal com- (3), Sr (4), Ba (5)] were readily prepared in high yield by two synthetic routes.…”

Section: Alkaline Earth Metal Complexes 3-5mentioning

confidence: 99%

Alkali Metal and Alkaline Earth Metal Complexes with the Bis(borane‐diphenylphosphanyl)amido Ligand – Synthesis, Structures, and Catalysis for Ring‐Opening Polymerization of ϵ‐Caprolactone

Bhattacharjee

Das

Reddy

et al. 2015

Zeitschrift anorg allge chemie

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Abstract. The syntheses of lithium and alkaline earth metal complexes with the bis(borane-diphenylphosphanyl)amido ligand (1-H) of molecular formulas [{κ 2 -N(PPh 2 (BH 3 )) 2 }Li(THF) 2 ] (2) and (3), Sr (4), Ba (5)] are reported. The lithium complex 2 was obtained by treatment of bis(borane-diphenylphosphanyl)amine (1-H) with lithium bis(trimethylsilyl)-amide in a 1:1 molar ratio via the silylamine elimination method. The corresponding homoleptic alkaline earth metal complexes 3-5 were prepared by two synthetic routes -first, the treatment of metal bis(trimethylsilyl)amide and protio ligand 1-H via the elimination of silylamine, and second, through salt metathesis reaction involving respective metal diiodides and lithium salt 2. The molecular structures of lithium complex 2 and barium complex 5 were established by

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“…The stoichiometry has to be met exactly in order to avoid halide‐containing products and also the formation of potassium calciates and their homologous derivatives. Popular examples include the silylated alkyl and benzyl complexes of the heavy alkaline earth metals . However, also tris(alkyl)calciate as well as tetrabenzylcalciate are known.…”

Section: Scope Of This Review and Introductionmentioning

confidence: 99%

Heavy Grignard Reagents: Synthesis, Physical and Structural Properties, Chemical Behavior, and Reactivity

Westerhausen

Koch

Görls

et al. 2016

Chemistry A European J

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The Grignard reaction offers a straight forward atom-economic synthesis of organomagnesium halides, which undergo redistribution reactions (Schlenk equilibrium) yielding diorganylmagnesium and magnesium dihalides. The homologous organocalcium complexes (heavy Grignard reagents) gained interest only quite recently owing to several reasons. The discrepancy between the inertness of this heavy alkaline earth metal and the enormous reactivity of its organometallics hampered a vast and timely development after the first investigation more than 100 years ago. In this overview the synthesis of organocalcium reagents is described as is the durability in ethereal solvents. Aryl-, alkenyl-, and alkylcalcium halides are prepared by direct synthesis. Characteristic structural features and NMR parameters are discussed. Ligand redistribution reactions can be performed by addition of potassium tert-butanolate to ethereal solutions of arylcalcium iodides yielding soluble diarylcalcium, whereas sparingly soluble potassium iodide and calcium bis(tert-butanolate) precipitate. Furthermore, reactivity studies with respect to metalation and addition to unsaturated organic compounds and metal-based Lewis acids, leading to the formation of heterobimetallic complexes, are presented.

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s-Block Organometallics: Analysis of Ion-Association and Noncovalent Interactions on Structure and Function in Benzyl-Based Compounds

Cited by 51 publications

References 153 publications

s‐Block Metal Complexes with Bis‐ and Tris(pyrazolyl)methane and ‐methanide Ligands

s‐Block Metal Complexes with Bis‐ and Tris(pyrazolyl)methane and ‐methanide Ligands

Alkali Metal and Alkaline Earth Metal Complexes with the Bis(borane‐diphenylphosphanyl)amido Ligand – Synthesis, Structures, and Catalysis for Ring‐Opening Polymerization of ϵ‐Caprolactone

Heavy Grignard Reagents: Synthesis, Physical and Structural Properties, Chemical Behavior, and Reactivity

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