New Ga/N‐based Active Lewis Pairs, Trifunctional Ga–Ga Compounds, Reactions with Cyanamide and Dual Insertion of Isocyanate

Uhl, Werner; Hengesbach, Frank; Isermann, Jennifer; Soleimani, Meisam; Schürmann, Lina; Hepp, Alexander; Layh, Marcus

doi:10.1002/zaac.201900195

Cited by 6 publications

(1 citation statement)

References 51 publications

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“…For 62 , these types of non‐cooperative ligand redox‐activity reaction modes were initiated for example by iodine, dibenzyl disulfide, or 3,6‐di‐ tert ‐butyl‐ ortho ‐benzoquinone[79b] as well as by acenaphthenequinone, sulfur dioxide, or azobenzene . Interestingly, the peculiar arrangement of the double addition product of 62 with C≡C triple bonds was also found elsewhere …”

Section: Group 13 Element‐ligand Cooperativitymentioning

confidence: 99%

Element‐Ligand Cooperativity with p‐Block Elements

et al. 2020

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Metal‐ligand cooperativity (MLC) had a tremendous impact on d‐block metal‐mediated bond activation and homogeneous catalysis. Is this concept translatable to the elements of the p‐block? Are there analogies already at hand? In this review, we describe contributions in which a p‐block element (group 13–15) and its ligand (surrounding molecular framework) operate synergistically in a substrate activation or a catalytic cycle. This activity is termed element‐ligand cooperativity (ELC), in correspondence to MLC. After the concepts of p‐block low‐valent states and frustrated Lewis pairs mimicking the ambiphilic reactivity of transition metals, the spatial proximity of nucleophilic and electrophilic reaction sites and a small HOMO‐LUMO gap in a p‐block ELC complex might offer yet another approach. Selected examples shall illustrate common reactivities of ELC, disclose conceptual analogies with d‐block MLC, and outline shortcomings in this field.

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Section: Group 13 Element‐ligand Cooperativitymentioning

confidence: 99%

Element‐Ligand Cooperativity with p‐Block Elements

et al. 2020

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Reactions of Al‐N Based Active Lewis Pairs with Ketones and 1,2‐Diketones: Insertion into Al‐N Bonds, C‐C and C‐N Bond Formation and a Tricyclic Saturated Tetraaza Compound

et al. 2020

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The monomeric aluminum hydrazide iBu 2 Al-N(C 10 H 15)(NC 5 H 10) (1) features a strained AlN 2 ring and is an efficient active Lewis pair. It reacted with 2,3-diphenyl-2-cyclopropen-1-one by insertion of the C=O group into an Al-N bond, cleavage of the C 3 ring and formation of an AlOC 3 heterocycle (2). Diacetyl, Me(O)C-C(O)Me, and 1 afforded by insertion of keto groups into both Al-N bonds a heterocyclic α-keto-hemihydrazinal coordinated to aluminum (3). 3 contains fused AlO 2 C 2 and C 2 N 2 heterocycles. In an unexpected reaction,

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Linear‐ and Cyclo‐Hexa(amino)hexaboranes: New Routes to Synthesis of B₆ Chain and B₆ Ring

Mesbah,

Berndt,

Soleimani

et al. 2024

Eur J Inorg Chem

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In this work, a linear‐hexaborane(8) B6(NMe2)6(CH2SiMe3)2 was synthesized using a new method. By replacing one chlorine atom of Cl2B3(NMe2)3 with CH2SiMe3 group, compound ClB3(NMe2)3CH2SiMe3 was prepared. Reductive dehalogenative coupling of ClB3(NMe2)3CH2SiMe3 led to linear‐hexaborane(8). Moreover, the six‐membered boron ring, cyclo‐hexaborane B6(NEt2)6 was synthesized by reductive dehalogenation of Br2BNEt2. The first linear‐hexaborane(8) and cyclo‐hexaborane B6(NEt2)6 crystal structures were fully characterized by X‐ray structural analysis and 11B, 1H, and 13C NMR spectroscopy. While the B1⋅⋅⋅⋅B6 chain in linear‐hexaborane(8) is strongly twisted at all B ̶ B bonds, the B6 ring cyclo‐hexaborane B6(NEt2)6 has a chair conformation similar to cyclohexane.

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New Ga/N‐based Active Lewis Pairs, Trifunctional Ga–Ga Compounds, Reactions with Cyanamide and Dual Insertion of Isocyanate

Abstract: Hydrogallation of Me 3 Si-CϵC-NR' 2 with R 2

Cited by 6 publications

References 51 publications

Element‐Ligand Cooperativity with p‐Block Elements

Element‐Ligand Cooperativity with p‐Block Elements

Reactions of Al‐N Based Active Lewis Pairs with Ketones and 1,2‐Diketones: Insertion into Al‐N Bonds, C‐C and C‐N Bond Formation and a Tricyclic Saturated Tetraaza Compound

Linear‐ and Cyclo‐Hexa(amino)hexaboranes: New Routes to Synthesis of B₆ Chain and B₆ Ring

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New Ga/N‐based Active Lewis Pairs, Trifunctional Ga–Ga Compounds, Reactions with Cyanamide and Dual Insertion of Isocyanate

Abstract: Hydrogallation of Me 3 Si-CϵC-NR' 2 with R 2

Cited by 6 publications

References 51 publications

Element‐Ligand Cooperativity with p‐Block Elements

Element‐Ligand Cooperativity with p‐Block Elements

Reactions of Al‐N Based Active Lewis Pairs with Ketones and 1,2‐Diketones: Insertion into Al‐N Bonds, C‐C and C‐N Bond Formation and a Tricyclic Saturated Tetraaza Compound

Linear‐ and Cyclo‐Hexa(amino)hexaboranes: New Routes to Synthesis of B6 Chain and B6 Ring

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Product

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About

Linear‐ and Cyclo‐Hexa(amino)hexaboranes: New Routes to Synthesis of B₆ Chain and B₆ Ring