Metal β-diketiminates revisited: ansa-CH2-bridged bis(β-diketiminate)s of lithium and aluminium having diverse structures

Bourget‐Merle, Laurence; Hitchcock, Peter B.; Läppert, Michael F.

doi:10.1016/j.jorganchem.2004.05.042

Cited by 24 publications

(19 citation statements)

References 16 publications

(16 reference statements)

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“…21 Lappert has created binucleating β-diketiminates that are linked through the backbone (3). 22 Other ligands that give two adjacent metal-binding sites similar to β-diketiminates have been reported. 23 Ligands with two-carbon linkers typically coordinate to a single metal like tetraazaannulenes: 24 for example, 4 gives mononuclear complexes.…”

Section: Introductionmentioning

confidence: 99%

Macrocyclic Binucleating β-Diketiminate Ligands and Their Lithium, Aluminum, and Zinc Complexes

et al. 2007

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The incorporation of rigid aromatic linkers into β-diketiminate ligands creates a binucleating scaffold that holds two metals near each other. This paper discloses the synthesis, characterization, and reactivity of mBin 2− , which has a meta-substituted xylylene spacer, and pBin 2− , which has a parasubstituted xylylene spacer. Lithium, aluminum, and zinc complexes of each ligand are isolated, and in some cases are characterized by X-ray crystallography. The lithium complexes are coordinated to solvent-derived THF ligands, while the zinc and aluminum complexes have alkyl ligands. Complexes of the mBin 2− ligand have an anti conformation in which the metals are on opposite sides of the macrocycle, while pBin 2− complexes prefer a syn conformation. The 1 H NMR spectra of the complexes demonstrate that the conformations rapidly interconvert in the lithium complexes, and less rapidly in the zinc and aluminum complexes.

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Section: Introductionmentioning

confidence: 99%

Macrocyclic Binucleating β-Diketiminate Ligands and Their Lithium, Aluminum, and Zinc Complexes

et al. 2007

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“…Bis(β‐diimine)s with various backbone‐substituents, including alkyl, aromatic, and disulfide bridges, are known today. The synthetic procedures differ to quite some extent (Scheme ) depending on the nature of the linker group.…”

Section: Bis(β‐diimine)smentioning

confidence: 99%

“…The synthetic procedures differ to quite some extent (Scheme ) depending on the nature of the linker group. An alkyl‐bridged bis(β‐diimine) is obtained when two equivalents of a lithium β‐diiminate are allowed to react with one equivalent of an alkyl dihalide (route iv ) . For aromatic bridges, two different routes have been applied: route v ) starts from bis(β‐dione)s and anilines, whereas route vi ) follows a rather complex sequence in which a bis(vinamidinium) salt is hydrolyzed and subsequent reaction with an aniline yields the desired bis(β‐diimine) .…”

Section: Bis(β‐diimine)smentioning

confidence: 99%

“…Three variants of backbone‐bridged bis(β‐diiminate)s have been so far reported in the literature. The heteroleptic complexes of type E are known for aluminum magnesium, and zinc, whereas examples of type E ′ complexes are known for aluminium and magnesium . Type F complexes are obtained when an additional ligand such as chlorido or n‐ butyl bridges the two metals (M=Fe, Mg, Zn) of complex E ′ .…”

Section: Bis(β‐diimine)smentioning

confidence: 99%

“…Type F complexes are obtained when an additional ligand such as chlorido or n‐ butyl bridges the two metals (M=Fe, Mg, Zn) of complex E ′ . Finally, also homoleptic backbone‐bridged cesium, lithium, and potassium complexes of type G are known, which nicely illustrates the effect of ligand and metal as the related aluminum, calcium, and magnesium complexes exists as type B , E , and E ′ complexes, respectively . Regarding the N‐bridged derivatives, an additional donor site within in the linker group affects the coordination behavior.…”

Section: Bis(β‐diimine)smentioning

confidence: 99%

See 2 more Smart Citations

Ligands with Two Monoanionic N,N‐Binding Sites: Synthesis and Coordination Chemistry

Kretschmer

2019

Chemistry A European J

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Polytopic ligands have become ubiquitous in coordination chemistry because they grant access to a variety of mono‐ and polynuclear complexes of transition metals as well as rare‐earth and main‐group elements. Nitrogen‐based ditopic ligands, in which two monoanionic N,N‐binding sites are framed within one molecule, are of particular importance and are therefore the primary focus of this review. In detail, bis(amidine)s, bis(guanidine)s, bis(β‐diimine)s, bis(aminotroponimine)s, bis(pyrrolimine)s, and miscellaneous bis(N,N‐chelating) ligands are reviewed. In addition to the general synthetic protocols, the application of these ligands is discussed along with their coordination chemistry, the multifarious binding modes, and the ability of these ligands to bridge two (or more) metal(loids).

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Resonance‐Assisted Hydrogen Bonding as a Driving Force in Synthesis and a Synthon in the Design of Materials

Mahmudov

Pombeiro

2016

Chemistry A European J

140

100

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Resonance-assisted hydrogen bonding (RAHB), a concept introduced by Gilli and co-workers in 1989, concerns a kind of intramolecular H-bonding strengthened by a conjugated π-system, usually in 6-, 8-, or 10-membered rings. This Review highlights the involvement of RAHB as a driving force in the synthesis of organic, coordination, and organometallic compounds, as a handy tool in the activation of covalent bonds, and in starting moieties for synthetic transformations. The unique roles of RAHB in molecular recognition and switches, E/Z isomeric resolution, racemization and epimerization of amino acids and chiral amino alcohols, solvatochromism, liquid-crystalline compounds, and in synthons for crystal engineering and polymer materials are also discussed. The Review can provide practical guidance for synthetic chemists that are interested in exploring and further developing RAHB-assisted synthesis and design of materials.

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Metal β-diketiminates revisited: ansa-CH2-bridged bis(β-diketiminate)s of lithium and aluminium having diverse structures

Cited by 24 publications

References 16 publications

Macrocyclic Binucleating β-Diketiminate Ligands and Their Lithium, Aluminum, and Zinc Complexes

Macrocyclic Binucleating β-Diketiminate Ligands and Their Lithium, Aluminum, and Zinc Complexes

Ligands with Two Monoanionic N,N‐Binding Sites: Synthesis and Coordination Chemistry

Resonance‐Assisted Hydrogen Bonding as a Driving Force in Synthesis and a Synthon in the Design of Materials

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