Addition of diphenylacetylene and methylvinylketone to aluminum complex of redox-active diimine ligand

Fedushkin, Igor L.; Moskalev, M. V.; Баранов, Е. В.; Abakumov, G. A.

doi:10.1016/j.jorganchem.2013.06.032

Cited by 33 publications

(19 citation statements)

References 23 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Cycloaddition of alkynes is also observed with aluminum dpp-Bian species: e.g., (dpp-Bian)AlEt(Et 2 O) and (dpp-Bian)Al–Al(dpp-Bian) . According to our observations the aluminum dpp-Bian complexes are in general more reactive toward alkynes in comparison to the gallium analogues.…”

Section: Introductionsupporting

confidence: 68%

Mononuclear dpp-Bian Gallium Complexes: Synthesis, Crystal Structures, and Reactivity toward Alkynes and Enones

et al. 2015

Self Cite

View full text Add to dashboard Cite

Treatment of (dpp-Bian)Ga−Ga(dpp-Bian) (1) (dpp-Bian = 1,2-bis [(2,6-diisopropylphenyl)imino]acenaphthene) with iodine gives (dpp-Bian)Ga(I)−Ga(I)-(dpp-Bian) (2 ), wh ich re act s in sit u wit h K-(C 5 H 4 CH 2 CH 2 NMe 2 ) (KCp Do ) or K(OCH 2 CH 2 NMe 2 ) (KOR Do ) to produce the monomeric species (dpp-Bian)-GaCp Do (3) and (dpp-Bian)GaOR Do (4), respectively. Complex 3 reacts with PhCCH to give the paramagnetic derivative (dpp-Bian)Ga(CCPh) 2 (5), while compound 4 is inert toward this alkyne. In contrast, monomeric (dpp-Bian)Ga(S 2 CNMe 2 ) (6) reacts with PhCCH and HCCH to give the cycloaddition products [dpp-Bian(PhC CH)]Ga(S 2 CNMe 2 ) ( 7) and [dpp-Bian(HCCH)]Ga(S 2 CNMe 2 ) (8). The related compounds [dpp-Bian(MeCCC(O)-OMe)]Ga(S 2 CNMe 2 ) ( 9) and [dpp-Bian(CH 2 CHC(Me)O)]Ga(S 2 CNMe 2 ) (10) have been obtained in the reactions of complex 6 with methyl 2-butynoate and methyl vinyl ketone, respectively. New complexes have been characterized by 1 H NMR (3, 4, and 7−10) and ESR (5) spectroscopy; their molecular structures have been established by single-crystal X-ray analysis. The catalytic activity of complex 6 in the hydroamination and hydroarylation of alkynes has been examined.

show abstract

Section: Introductionsupporting

confidence: 68%

Mononuclear dpp-Bian Gallium Complexes: Synthesis, Crystal Structures, and Reactivity toward Alkynes and Enones

et al. 2015

Self Cite

View full text Add to dashboard Cite

show abstract

“…An exception was provided by diphenylamine as substrate, which hampered adduct formation due to increased steric demand. Surprisingly, the hydroarylation with phenylacetylene was possible with 30 as catalyst (Figure a), but not with digallane 62 . Moreover, dialane 30 rendered suitable as a catalyst for the ring‐opening polymerization of ε‐caprolactone (Figure b) .…”

Section: Group 13 Element‐ligand Cooperativitymentioning

confidence: 99%

“…In contrast, digallane 62 showed reversible 1,2‐addition with methyl but‐2‐yonate without breaking the Ga–Ga bond. Besides the dipp‐bian‐supported dinuclear Al(II) complex 30 , the related mononuclear Al(III) complex 33 was studied (Figure b) . The reaction of 33 with methyl vinyl ketone proceeded at ambient temperature and resulted in 1,4‐addition to the α,β‐unsaturated substrate to give 34 .…”

Section: Group 13 Element‐ligand Cooperativitymentioning

confidence: 99%

See 1 more Smart Citation

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

“…Recently, redox-active ligand-assisted two-electron oxidative addition of organic halides to gallium centers in digallane has been achieved . One of the most notable chemical transformations of organic substrates on group 13 metal complexes of dpp-dad and dpp-Bian ligands is cycloaddition of alkynes, alkenes, conjugated enones, isocyanates, and isothiocyanates to LM–ML (L = dpp-dad or dpp-Bian; M = Al, Ga) − as well as to some related mononuclear gallium and aluminum derivatives. − Most of these reactions feature notable chemo-, regio-, and stereoselectivity and, surprisingly, occur reversibly. One may expect that NHCs may alter reactivity of group 13 metal complexes of redox-active ligands.…”

Section: Introductionmentioning

confidence: 99%

Reactivity of Aluminum Complexes of Redox-Active Ligand toward N-Heterocyclic Carbene and Its Thione

et al. 2019

Self Cite

View full text Add to dashboard Cite

The reaction of dialane (dpp-Bian)Al−Al(dpp-Bian) (1) (dpp-Bian is dianion of 1,2-bis [(2,6diisopropylphenyl)imino]-acenaphthene) with 1 mol equiv of 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (iPr 2 Im Me ) results in the Al-carbene adduct (dpp-Bian)(iPr 2 Im Me )Al− Al(dpp-Bian) (3). In the course of the reaction of dialane 1 with 2 mol equiv of 1,3-diisopropyl-4,5-dimethylimidazol-2thione (iPr 2 Imt Me ) a half of the thione amount undergoes a cleavage of sulfur−carbon double bond. In the product (dpp-Bian)(iPr 2 Im Me )Al(μ-S)Al(iPr 2 Imt Me )(dpp-Bian) (4) aluminum atoms coordinate carbene as well as thione ligands. Compound 4 is thermally robust: no reduction of CS bond in thione moiety by the dpp-Bian ligands could be observed in toluene for 24 h at 100 °C. Complex {(dpp-Bian)(iPr 2 Im Me )Al} 2 (μ-S) (5) was isolated from the reaction of dialane 1, iPr 2 Im Me , and iPr 2 Imt Me (1:1:1). The reaction of mononuclear (dpp-Bian)AlH(THF) (2) (THF = tetrahydrofuran) affords compound (dpp-Bian)AlH(iPr 2 Im Me ) (6). Compounds 3−6 were characterized by 1 H NMR and IR spectroscopy; their molecular structures were established by single-crystal X-ray analysis.

show abstract

Addition of diphenylacetylene and methylvinylketone to aluminum complex of redox-active diimine ligand

Cited by 33 publications

References 23 publications

Mononuclear dpp-Bian Gallium Complexes: Synthesis, Crystal Structures, and Reactivity toward Alkynes and Enones

Mononuclear dpp-Bian Gallium Complexes: Synthesis, Crystal Structures, and Reactivity toward Alkynes and Enones

Element‐Ligand Cooperativity with p‐Block Elements

Reactivity of Aluminum Complexes of Redox-Active Ligand toward N-Heterocyclic Carbene and Its Thione

Contact Info

Product

Resources

About