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

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Abstract

The reactions of two equivalents of germylene [(i-Pr)2NB(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)2NB(N-2,6-Me2C6H3)2]Ge(DMAP) (5) was isolated, but using t-BuNC resulted in the formation of germanium(IV) cyanide [(i-Pr)2NB(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)2NB(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.

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

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Article information


Submitted
20 Dec 2019
Accepted
06 Mar 2020
First published
06 Mar 2020

Dalton Trans., 2020, Advance Article
Article type
Paper

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

J. Böserle, R. Jambor, A. Růžička, M. Erben and L. Dostál, Dalton Trans., 2020, Advance Article , DOI: 10.1039/C9DT04839A

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