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 3 publications

(1 citation statement)

References 51 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…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

View full text Add to dashboard Cite

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.

show abstract

Section: Group 13 Element‐ligand Cooperativitymentioning

confidence: 99%

Element‐Ligand Cooperativity with p‐Block Elements

et al. 2020

View full text Add to dashboard Cite

show abstract

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

Self Cite

View full text Add to dashboard Cite

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,

show abstract

Al/N-based active Lewis pairs: isocyanate insertion products as efficient nucleophiles employed for the facile generation of highly functional molecules

Horstmann

Hepp

Layh

et al. 2020

Zeitschrift Für Naturforschung B

View full text Add to dashboard Cite

AbstractThe previously reported active Lewis pair (ALP) iBu2Al–N(2-Ad)NC5H10 (1) (2-Ad = 2-adamantyl) is readily accessible by hydroalumination of the hydrazone H10C5N–N=(2-C10H14) with H–AliBu2. Treatment of 1 with two equivalents of isocyanates R-N=C=O yields six-membered AlC2N2O heterocycles 2 (2a, R = Ph; 2b, R = p-Tol) by dual insertion into the Al–N bonds. 2a reacts as a nucleophile with carboxylic acid chlorides R-C(O)–Cl [R = CH2tBu, p-Tol, H2CCH(Me)C6H4(4-CH2CHMe2) (Ibu-profen acid chloride), 0.5 (1,4-C6H4)] to afford by elimination of iBu2AlCl and hydrolysis new triuret derivatives R-C(O)[N(Ph)C(O)]2–N(2-Ad)NC5H10 (3a to 3d) as colourless, sparingly soluble solids in moderate (3c) to high (3b) yields. The analogous reaction of 2a with (p-Tol)–C(Cl)=N(p-Tol) leads to the imidoyl derivative (p-Tol)N=C(p-Tol)[N(Ph)C(O)]2–N(2-Ad)NC5H10 (4a), which showed a fast exchange of phenyl and tolyl groups to yield a mixture of isomers. The analogous reaction of 2b affords the corresponding compound 4b for which a single isomer is isolated despite the scrambling of substituents.

show abstract

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 3 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

Al/N-based active Lewis pairs: isocyanate insertion products as efficient nucleophiles employed for the facile generation of highly functional molecules

Contact Info

Product

Resources

About