Different Products of the Reduction of (N),C,N-Chelated Antimony(III) Compounds: Competitive Formation of Monomeric Stibinidenes versus 1H-2,1-Benzazastiboles

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216275%3A25310%2F17%3A39911697" target="_blank" >RIV/00216275:25310/17:39911697 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1002/chem.201604142" target="_blank" >http://dx.doi.org/10.1002/chem.201604142</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/chem.201604142" target="_blank" >10.1002/chem.201604142</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Different Products of the Reduction of (N),C,N-Chelated Antimony(III) Compounds: Competitive Formation of Monomeric Stibinidenes versus 1H-2,1-Benzazastiboles

Popis výsledku v původním jazyce

The reduction of N,C,N-chelated antimony(III) chlorides [C6H3-2,6-(CH=NR)(2)]SbCl2 (R=Ph (1), tBu (2), Dip (3); Dip=2,6-iPr(2)C(6)H(3)) with an appropriate amount of KC8 or Li[AlH4] resulted in the formation of rare examples of monomeric stibinidenes [C6H3-2,6-(CH=NR)(2)]Sb (R=Ph (4), tBu (5), Dip (6)). Similarly, the reduction of compounds 1 or 2 by two equivalents of K[B(sBu)(3)H] led to the stibinidenes 4 and 5. In contrast, the analogous reaction of compound 3 resulted in the formation of an unprecedented stibinidene [C6H3-2-(CH=NR)-6-(CH2NHR)]Sb (7) (R=Dip), in which the hydrogen atoms that come from the K[B(sBu)(3)H] are incorporated into the ligand backbone. To gain further insight into this intriguing reactivity with K[B(sBu)(3)H] and to assess the influence of the substitution at both the antimony atom and pendant substituents, we prepared compounds [C6H3-2-(CH=NDip)]Sb(Ph)Cl (8) and [C6H2-2-(CH=NDip)-4,6-(tBu)(2)]SbCl2 (9). The treatment of compound 8 with K[B(sBu)(3)H] smoothly led to the 1-Ph-2-Dip-1H-2,1-benzazastibole (11), whereas the reaction of compound 9 with K[B(sBu)(3)H] resulted in either tBu-substituted 1-Cl-2-Dip-1H-2,1-benzazastibole (13) or the formation of unprecedented Sb-Sb dimer bis(2-Dip-1H-2,1-benzazastibole) (12) depending on the reaction stoichiometry. The miscellaneous reactivity of antimony(III) precursors with reducing agents together with the structure and bonding of the resulting products has also been investigated from a theoretical point of view.

Název v anglickém jazyce

Different Products of the Reduction of (N),C,N-Chelated Antimony(III) Compounds: Competitive Formation of Monomeric Stibinidenes versus 1H-2,1-Benzazastiboles

Popis výsledku anglicky

The reduction of N,C,N-chelated antimony(III) chlorides [C6H3-2,6-(CH=NR)(2)]SbCl2 (R=Ph (1), tBu (2), Dip (3); Dip=2,6-iPr(2)C(6)H(3)) with an appropriate amount of KC8 or Li[AlH4] resulted in the formation of rare examples of monomeric stibinidenes [C6H3-2,6-(CH=NR)(2)]Sb (R=Ph (4), tBu (5), Dip (6)). Similarly, the reduction of compounds 1 or 2 by two equivalents of K[B(sBu)(3)H] led to the stibinidenes 4 and 5. In contrast, the analogous reaction of compound 3 resulted in the formation of an unprecedented stibinidene [C6H3-2-(CH=NR)-6-(CH2NHR)]Sb (7) (R=Dip), in which the hydrogen atoms that come from the K[B(sBu)(3)H] are incorporated into the ligand backbone. To gain further insight into this intriguing reactivity with K[B(sBu)(3)H] and to assess the influence of the substitution at both the antimony atom and pendant substituents, we prepared compounds [C6H3-2-(CH=NDip)]Sb(Ph)Cl (8) and [C6H2-2-(CH=NDip)-4,6-(tBu)(2)]SbCl2 (9). The treatment of compound 8 with K[B(sBu)(3)H] smoothly led to the 1-Ph-2-Dip-1H-2,1-benzazastibole (11), whereas the reaction of compound 9 with K[B(sBu)(3)H] resulted in either tBu-substituted 1-Cl-2-Dip-1H-2,1-benzazastibole (13) or the formation of unprecedented Sb-Sb dimer bis(2-Dip-1H-2,1-benzazastibole) (12) depending on the reaction stoichiometry. The miscellaneous reactivity of antimony(III) precursors with reducing agents together with the structure and bonding of the resulting products has also been investigated from a theoretical point of view.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

<a href="/cs/project/GA15-06609S" target="_blank" >GA15-06609S: Organokovové sloučeniny antimonné a bismutné - nová třída ligandů pro přechodné kovy</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2017

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Chemistry - A European Journal

ISSN

0947-6539

e-ISSN

—

Svazek periodika

23

Číslo periodika v rámci svazku

10

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

10

Strana od-do

2340-2349

Kód UT WoS článku

000395583200017

EID výsledku v databázi Scopus

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