Reactivity of boraguanidinato germylenes toward carbonyl compounds and isocyanides: C-O, C-F and C-N bond activation

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216275%3A25310%2F20%3A39916595" target="_blank" >RIV/00216275:25310/20:39916595 - isvavai.cz</a>

Výsledek na webu

<a href="https://doi.org/10.1039/C9DT04839A" target="_blank" >https://doi.org/10.1039/C9DT04839A</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/c9dt04839a" target="_blank" >10.1039/c9dt04839a</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Reactivity of boraguanidinato germylenes toward carbonyl compounds and isocyanides: C-O, C-F and C-N bond activation

Popis výsledku v původním jazyce

The reactions of two equivalents of germylene [(i-Pr)(2)NB(N-2,6-Me2C6H3)(2)]Ge (1) with carbonyl compounds RC(O)R &apos; resulted in carbonyl functionality activation and the formation of 4-(R,R &apos;)-1,2-digerma-3-oxa-cyclobutanes (R/R &apos; = Ph/CF3 (2) or C6F5/H (3)). Surprisingly, the analogous reaction of 1 with C6F5C(O)Me led to the insertion of the germanium atom into the C-F bond of the perfluorophenyl group, thus producing a spiro compound (4) with a germanium atom sharing 1,2-digerma-3,5-diaza-4-bora-cyclopentane and 1-germa-2,4-diaza-3-boracyclobutane rings. Furthermore, the reaction of 1 with 2e(-) donors was investigated. In the case of 4-dimethylaminopyridine (DMAP), an expected complex [(i-Pr)(2)NB(N-2,6-Me2C6H3)(2)]Ge(DMAP) (5) was isolated, but using t-BuNC resulted in the formation of germanium(iv) cyanide [(i-Pr)(2)NB(N-2,6-Me2C6H3)(2)]Ge(CN)(t-Bu) (6) as a result of C-N bond activation in the starting isocyanide. In contrast, mixing other isocyanides RNC (R = Cy or Ad) with 1 in solution led only to an equilibrium between the starting compounds and most probably the corresponding complexes [(i-Pr)(2)NB(N-2,6-Me2C6H3)(2)]Ge(CNR) (R = Cy (7a) or Ad (8a)) based on NMR studies. From these equilibrium mixtures, fortuitously, single crystals of digerma-spiro-complexes (7 and 8) containing two germanium atoms (one of them coordinated to a particular isocyanide) were obtained and structurally authenticated by the X-ray diffraction technique.

Název v anglickém jazyce

Reactivity of boraguanidinato germylenes toward carbonyl compounds and isocyanides: C-O, C-F and C-N bond activation

Popis výsledku anglicky

The reactions of two equivalents of germylene [(i-Pr)(2)NB(N-2,6-Me2C6H3)(2)]Ge (1) with carbonyl compounds RC(O)R &apos; resulted in carbonyl functionality activation and the formation of 4-(R,R &apos;)-1,2-digerma-3-oxa-cyclobutanes (R/R &apos; = Ph/CF3 (2) or C6F5/H (3)). Surprisingly, the analogous reaction of 1 with C6F5C(O)Me led to the insertion of the germanium atom into the C-F bond of the perfluorophenyl group, thus producing a spiro compound (4) with a germanium atom sharing 1,2-digerma-3,5-diaza-4-bora-cyclopentane and 1-germa-2,4-diaza-3-boracyclobutane rings. Furthermore, the reaction of 1 with 2e(-) donors was investigated. In the case of 4-dimethylaminopyridine (DMAP), an expected complex [(i-Pr)(2)NB(N-2,6-Me2C6H3)(2)]Ge(DMAP) (5) was isolated, but using t-BuNC resulted in the formation of germanium(iv) cyanide [(i-Pr)(2)NB(N-2,6-Me2C6H3)(2)]Ge(CN)(t-Bu) (6) as a result of C-N bond activation in the starting isocyanide. In contrast, mixing other isocyanides RNC (R = Cy or Ad) with 1 in solution led only to an equilibrium between the starting compounds and most probably the corresponding complexes [(i-Pr)(2)NB(N-2,6-Me2C6H3)(2)]Ge(CNR) (R = Cy (7a) or Ad (8a)) based on NMR studies. From these equilibrium mixtures, fortuitously, single crystals of digerma-spiro-complexes (7 and 8) containing two germanium atoms (one of them coordinated to a particular isocyanide) were obtained and structurally authenticated by the X-ray diffraction technique.

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/GA17-10377S" target="_blank" >GA17-10377S: Multideprotonovatelné, ambifilické a hybridní ligandy s uspořádáním vhodným pro tvorbu oligometalických komplexů kovů</a><br>

Návaznosti

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

Rok uplatnění

2020

Kód důvěrnosti údajů

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

Název periodika

Dalton Transactions

ISSN

1477-9226

e-ISSN

—

Svazek periodika

49

Číslo periodika v rámci svazku

15

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

9

Strana od-do

4869-4877

Kód UT WoS článku

000527540400025

EID výsledku v databázi Scopus

2-s2.0-85083544782