Simple Alkaline‐Earth Metal Catalysts for Effective Alkene Hydrogenation

Bauer, Horst; Alonso, Mercedes; Fischer, Christian; Rösch, Bastian; Elsen, Holger; Harder, Sjoerd

doi:10.1002/ange.201810026

Cited by 33 publications

(3 citation statements)

References 41 publications

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“…[22] Its strontium analogue,[ {BDI DiPP }Sr-(thf)(m-F) 2 Sr{BDI DiPP }(thf) 2 ], is asymmetrically ligated:o ne Sr atom bears one coordinated thf molecule,a nd the other carries two of them [Sr-F = 2.348(1) av ]. [25] The 19 S22) revealed ad istorted tetrahedral geometry around potassium, with K-N interatomic distances [2.6479(11)-2.7332 (11) ]within the known ranges for potassium diiminocarbazolates. [38] Thes toichiometric reaction of [{Carb DiPP }K•(thf) 2 ]a nd BaI 2 in thf affords [{Carb DiPP }BaI•(thf) 2 ](3)asayellow solid in near quantitative yield (see Scheme 1).…”

Section: Resultsmentioning

confidence: 78%

Bis(imino)carbazolate: A Master Key for Barium Chemistry

et al. 2020

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Reported here is ar eadily available bis-(imino)carbazole-based proligand that constitutes aconvenient entry point into the challenging synthetic molecular chemistry of barium. It enables the preparation of rare or even, up to now, unknown, solution-stable heteroleptic barium complexes.T he syntheses and structural features for the first molecular barium fluoride and the first barium stannylide,w ith an unsupported BaÀSn bond, are described, along with other carbazolate barium species:a na mide (both ar emarkably stable starting material and an excellent hydrophosphination precatalyst), iodide,and silanylide.DFT analysis of bonding patterns in the barium stannylide and barium silanylide highlights ap revailingly ionic barium-tetrelide bond with as mall covalent contribution.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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Section: Resultsmentioning

confidence: 78%

Bis(imino)carbazolate: A Master Key for Barium Chemistry

et al. 2020

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“…[22] Its strontium analogue,[ {BDI DiPP }Sr-(thf)(m-F) 2 Sr{BDI DiPP }(thf) 2 ], is asymmetrically ligated:o ne Sr atom bears one coordinated thf molecule,a nd the other carries two of them [Sr-F = 2.348(1) av ]. [25] The 19 Figure S22) revealed ad istorted tetrahedral geometry around potassium, with K-N interatomic distances [2.6479(11)-2.7332 (11) ]within the known ranges for potassium diiminocarbazolates. [38] (Figure 4).…”

Section: Forschungsartikelmentioning

confidence: 79%

“…These issues are generally overcome by using bulky chelating ancillary ligands to inhibit Schlenk redistribution into homoleptic species that are either unreactive or uncontrollably reactive,o ri nto insoluble polynuclear species.H owever,e xcept for af ew examples, the limited range of appropriate ligands has hampered the use of these metals in organometallic processes,especially for the largest and most electropositive barium. Despite the problems associated with Ae metals,m any examples exist in the recent literature of catalytic processes using low Ae catalyst loadings and mild reaction conditions, [1][2][3][4] for example,olefin hydroelementation, [7][8][9] imine [10] or alkene [11] hydrogenation, and dehydrocoupling of amines with either hydrosilanes [12] or boranes. [13] Fort he chemistry of the heavier Ae metals,n o ligand is more ubiquitous than 2,6-bis-diisopropylphenyl-b-diketiminate (BDI DiPP ,F igure 1).…”

Section: Introductionmentioning

confidence: 99%

Bis(imino)carbazolate: A Master Key for Barium Chemistry

et al. 2020

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Reported here is a readily available bis(imino)carbazole‐based proligand that constitutes a convenient entry point into the challenging synthetic molecular chemistry of barium. It enables the preparation of rare or even, up to now, unknown, solution‐stable heteroleptic barium complexes. The syntheses and structural features for the first molecular barium fluoride and the first barium stannylide, with an unsupported Ba−Sn bond, are described, along with other carbazolate barium species: an amide (both a remarkably stable starting material and an excellent hydrophosphination precatalyst), iodide, and silanylide. DFT analysis of bonding patterns in the barium stannylide and barium silanylide highlights a prevailingly ionic barium–tetrelide bond with a small covalent contribution.

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Alkene Transfer Hydrogenation with Alkaline‐Earth Metal Catalysts

et al. 2019

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The alkene transfer hydrogenation (TH) of avariety of alkenes has been achieved with simple AeN'' 2 catalysts [Ae = Ca, Sr,B a; N'' = N(SiMe 3 ) 2 ]u sing 1,4-cyclohexadiene (1,4-CHD) as aHsource.R eaction of 1,4-CHD with AeN'' 2 gave benzene,N''H, and the metal hydride species N''AeH (or aggregates thereof), whichi sacatalyst for alkene hydrogenation. BaN'' 2 is by far the most active catalyst. Hydrogenation of activated C=Cb onds (e.g. styrene) proceeded at room temperature without polymer formation. Unactivated (isolated) C=Cbonds (e.g. 1-hexene) needed ahigher temperature (120 8 8C) but proceeded without double-bond isomerization. The ligands fully control the course of the catalytic reaction, which can be:1 )alkene TH, 2) 1,4-CHD dehydrogenation, or 3) alkene polymerization. DFT calculations support formation of ametal hydride species by deprotonation of 1,4-CHD followed by Ht ransfer.C onvenient access to larger quantities of BaN'' 2 ,its high activity and selectivity,and the many advantages of TH make this as imple but attractive procedure for alkene hydrogenation. Scheme 1. Various concepts for transfer hydrogenation.

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Simple Alkaline‐Earth Metal Catalysts for Effective Alkene Hydrogenation

Cited by 33 publications

References 41 publications

Bis(imino)carbazolate: A Master Key for Barium Chemistry

Bis(imino)carbazolate: A Master Key for Barium Chemistry

Bis(imino)carbazolate: A Master Key for Barium Chemistry

Alkene Transfer Hydrogenation with Alkaline‐Earth Metal Catalysts

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