Hydrido‐Komplexe des Calciums: eine neue Familie molekularer Erdalkalimetall‐Verbindungen

Mukherjee, Debabrata; Schuhknecht, Danny; Okuda, Jun

doi:10.1002/ange.201801869

Cited by 23 publications

(1 citation statement)

References 116 publications

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“…Although the organometallic chemistry of the heavier group 2a lkaline-earth metals (Ae = Ca, Sr, Ba) has received considerable attention in the past two decades, [1][2][3][4][5][6] it still lags behind the chemistry of transition metals and that of the lanthanides.T his is primarily due to the extreme oxophillic nature of the Ae metals,t heir strong ionic character,a nd hence their tendencyt or edistribute ligands in solution through aS chlenk equilibrium. 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.…”

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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Section: Introductionmentioning

confidence: 99%

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

et al. 2020

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Low‐Coordinate Barium Boryloxides: Synthesis and Dehydrocoupling Catalysis for the Production of Borasiloxanes

et al. 2018

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The first soluble barium boryloxides [Ba]– OB{CH(SiMe3)2} are presented. These mono‐ or dinuclear complexes feature low coordination numbers, as low as two for [Ba(OB{CH(SiMe3)2}2)2], which is further stabilized by intra‐ and intermolecular Ba⋅⋅⋅H3C agostic interactions. Barium boryloxides and the parent [Ba{N(SiMe3)2}2⋅(thf)2] catalyze the dehydrocoupling of borinic acids with hydrosilanes, providing borasiloxanes under mild conditions.

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Heterolysis of Dihydrogen by Nucleophilic Calcium Alkyls

et al. 2018

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b-Diketiminato (BDI) calcium alkyl derivatives undergo hydrogenolysis with H 2 to regenerate [(BDI)CaH] 2 , allowing the catalytic hydrogenation of aw ide range of 1alkenes and norbornene under very mild conditions (2 bar H 2 , 298 K). The reactions are deduced to take place with the retention of the dimeric structures of the calcium hydrido-alkyl and alkyl intermediates via aw ell-defined sequence of CaÀH/ C = Ci nsertion and Ca À Ch ydrogenation events.T his latter deduction is strongly supported by DFT calculations (B3PW91) performed on the 1-hexene/H 2 system, which also indicates that the hydrogenation transition states display features whichd iscriminate them from ac lassical s-bond metathesis mechanism. In particular,N BO analysis identifies as trong second order interaction between the filled amethylene sp 3 orbital of the n-hexyl chain and the s*o rbital of the H 2 molecule,signifying that the H À Hbond is broken by what is effectively the nucleophilic displacement of hydride by the organic substituent.Thecatalytichydrogenationofalkenesandalkynesbymidto late transition metal complexes has been developed to ahigh degree of sophistication and is typically predicated on the cooperative binding and activation of both unsaturated hydrocarbons and H 2 at ar edox-active metal center. [1][2][3][4][5][6][7][8][9] Albeit less well developed, similar catalysis was achieved by group 3and organolanthanide complexes more than aquarter of ac entury ago. [10][11][12][13][14] In these latter cases,ad 0 electron configuration mitigates against redox-based reactivity and turnover is derived from alkene insertion into ap olarised metal-hydrogen bond to form an alkyl intermediate,which is itself reactive toward H 2 through s-bond metathesis to release the hydrocarbon and regenerate the active hydride catalyst.

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Hydrido‐Komplexe des Calciums: eine neue Familie molekularer Erdalkalimetall‐Verbindungen

Cited by 23 publications

References 116 publications

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

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

Low‐Coordinate Barium Boryloxides: Synthesis and Dehydrocoupling Catalysis for the Production of Borasiloxanes

Heterolysis of Dihydrogen by Nucleophilic Calcium Alkyls

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