Reactivity of boraguanidinato germylenes toward carbonyl compounds and isocyanides: C-O, C-F and C-N bond activation
The result's identifiers
Result code in 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>
Result on the web
<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>
Alternative languages
Result language
angličtina
Original language name
Reactivity of boraguanidinato germylenes toward carbonyl compounds and isocyanides: C-O, C-F and C-N bond activation
Original language description
The reactions of two equivalents of germylene [(i-Pr)(2)NB(N-2,6-Me2C6H3)(2)]Ge (1) with carbonyl compounds RC(O)R ' resulted in carbonyl functionality activation and the formation of 4-(R,R ')-1,2-digerma-3-oxa-cyclobutanes (R/R ' = 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.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10402 - Inorganic and nuclear chemistry
Result continuities
Project
<a href="/en/project/GA17-10377S" target="_blank" >GA17-10377S: Multideprotonable, ambiphilic and hybrid ligands with appropriate shape and electron pool for formation of oligometallic complexes</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2020
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Dalton Transactions
ISSN
1477-9226
e-ISSN
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Volume of the periodical
49
Issue of the periodical within the volume
15
Country of publishing house
GB - UNITED KINGDOM
Number of pages
9
Pages from-to
4869-4877
UT code for WoS article
000527540400025
EID of the result in the Scopus database
2-s2.0-85083544782