Synthesis and characterization of the heavy alkaline earth aryloxide congeners

Boyle, Timothy J.; Steele, Leigh Anna Marie; Saad, Alia

doi:10.1016/j.ica.2012.07.019

Cited by 5 publications

(2 citation statements)

References 34 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…50 These distances are within reasonable limits of what others have observed. 30–33,51,52 The K⋯K distance at 3.939 Å is longer than that of Na⋯Na in 2 (3.320 Å). The distance is shorter than the distances (4.39–4.77 Å) found for other solvents or chloro-bridged binuclear K complexes.…”

Section: Resultsmentioning

confidence: 97%

“…The distance is shorter than the distances (4.39-4.77 Å) found for other solvents or chlorobridged binuclear K complexes. 51,52 The shorter lengths suggest less steric strain on the potassium ions. The other significant difference with 1 is that the binding of K2 to multiple Fe(III) bis complex gave rise to a corrugated sheet-like 2D network (Fig.…”

Section: Dalton Transactions Papermentioning

confidence: 99%

See 1 more Smart Citation

Water-soluble chiral coordination polymers of Li⁺, Na⁺, K⁺, and Ba²⁺ with an anionic iron(iii) complex of a l-threonine derivative and a significant red shift of visible spectra with Al³⁺ salt

Long,

Ray

2024

Dalton Trans.

View full text Add to dashboard Cite

show abstract

Section: Resultsmentioning

confidence: 97%

Section: Dalton Transactions Papermentioning

confidence: 99%

Water-soluble chiral coordination polymers of Li⁺, Na⁺, K⁺, and Ba²⁺ with an anionic iron(iii) complex of a l-threonine derivative and a significant red shift of visible spectra with Al³⁺ salt

Long,

Ray

2024

Dalton Trans.

View full text Add to dashboard Cite

show abstract

Heavier Alkaline‐Earth Catalyzed Dehydrocoupling of Silanes and Alcohols for the Synthesis of Metallo‐Polysilylethers

Morris

Hill

Mahon

et al. 2020

Chemistry A European J

View full text Add to dashboard Cite

The dehydrocoupling of silanes and alcohols mediated by heavier alkaline‐earth catalysts, [Ae{N(SiMe3)2}2⋅(THF)2] (I–III) and [Ae{CH(SiMe3)2}2⋅(THF)2], (IV–VI) (Ae=Ca, Sr, Ba) is described. Primary, secondary, and tertiary alcohols were coupled to phenylsilane or diphenylsilane, whereas tertiary silanes are less tolerant towards bulky substrates. Some control over reaction selectivity towards mono‐, di‐, or tri‐substituted silylether products was achieved through alteration of reaction stoichiometry, conditions, and catalyst. The ferrocenyl silylether, FeCp(C5H4SiPh(OBn)2) (2), was prepared and fully characterized from the ferrocenylsilane, FeCp(C5H4SiPhH2) (1), and benzyl alcohol using barium catalysis. Stoichiometric experiments suggested a reaction manifold involving the formation of Ae–alkoxide and hydride species, and a series of dimeric Ae–alkoxides [(Ph3CO)Ae(μ2‐OCPh3)Ae(THF)] (3 a–c, Ae=Ca, Sr, Ba) were isolated and fully characterized. Mechanistic experiments suggested a complex reaction mechanism involving dimeric or polynuclear active species, whose kinetics are highly dependent on variables such as the identity and concentration of the precatalyst, silane, and alcohol. Turnover frequencies increase on descending Group 2 of the periodic table, with the barium precatalyst III displaying an apparent first‐order dependence in both silane and alcohol, and an optimum catalyst loading of 3 mol % Ba, above which activity decreases. With precatalyst III in THF, ferrocene‐containing poly‐ and oligosilylethers with ferrocene pendent to‐ (P1–P4) or as a constituent (P5, P6) of the main polymer chain were prepared from 1 or Fe(C5H4SiPhH2)2 (4) with diols 1,4‐(HOCH2)2‐(C6H4) and 1,4‐(CH(CH3)OH)2‐(C6H4), respectively. The resultant materials were characterized by NMR spectroscopy, gel permeation chromatography (GPC) and DOSY NMR spectroscopy, with estimated molecular weights in excess of 20,000 Da for P1 and P4. The iron centers display reversible redox behavior and thermal analysis showed P1 and P5 to be promising precursors to magnetic ceramic materials.

show abstract

Contemporary Molecular Barium Chemistry

Chapple

Sarazin

2020

Eur J Inorg Chem

View full text Add to dashboard Cite

Driven by the many potential applications as molecular catalyst for a range of metal‐promoted transformations, the quest for well‐defined, soluble and reactive complexes of barium has attracted substantial interest in the past decade. While it has long been overlooked, barium is now one of the hotly debated metals in main group chemistry. The present review surveys the main achievements of the last 10 years in the molecular chemistry of barium, presenting along the way the key synthetic strategies that have been implemented successfully to address the specificities of barium chemistry. This includes ligand design and non‐covalent interactions. The performances of barium complexes as homogeneous catalysts for the most prominent reactions mediated by alkaline‐earth metals (hydroelementations and heterodehydrocouplings) are reviewed in conjunction with those obtained with somewhat more common calcium or strontium catalysts.

show abstract

Synthesis and characterization of the heavy alkaline earth aryloxide congeners

Cited by 5 publications

References 34 publications

Water-soluble chiral coordination polymers of Li⁺, Na⁺, K⁺, and Ba²⁺ with an anionic iron(iii) complex of a l-threonine derivative and a significant red shift of visible spectra with Al³⁺ salt

Water-soluble chiral coordination polymers of Li⁺, Na⁺, K⁺, and Ba²⁺ with an anionic iron(iii) complex of a l-threonine derivative and a significant red shift of visible spectra with Al³⁺ salt

Heavier Alkaline‐Earth Catalyzed Dehydrocoupling of Silanes and Alcohols for the Synthesis of Metallo‐Polysilylethers

Contemporary Molecular Barium Chemistry

Contact Info

Product

Resources

About

Synthesis and characterization of the heavy alkaline earth aryloxide congeners

Cited by 5 publications

References 34 publications

Water-soluble chiral coordination polymers of Li+, Na+, K+, and Ba2+ with an anionic iron(iii) complex of a l-threonine derivative and a significant red shift of visible spectra with Al3+ salt

Water-soluble chiral coordination polymers of Li+, Na+, K+, and Ba2+ with an anionic iron(iii) complex of a l-threonine derivative and a significant red shift of visible spectra with Al3+ salt

Heavier Alkaline‐Earth Catalyzed Dehydrocoupling of Silanes and Alcohols for the Synthesis of Metallo‐Polysilylethers

Contemporary Molecular Barium Chemistry

Contact Info

Product

Resources

About

Water-soluble chiral coordination polymers of Li⁺, Na⁺, K⁺, and Ba²⁺ with an anionic iron(iii) complex of a l-threonine derivative and a significant red shift of visible spectra with Al³⁺ salt

Water-soluble chiral coordination polymers of Li⁺, Na⁺, K⁺, and Ba²⁺ with an anionic iron(iii) complex of a l-threonine derivative and a significant red shift of visible spectra with Al³⁺ salt