TY  - JOUR
A1  - Häring, Mathias
A1  - Kerpen, Christoph
A1  - Ribbeck, Tatjana
A1  - Hennig, Philipp T.
A1  - Bertermann, Rüdiger
A1  - Ignat’ev, Nikolai V.
A1  - Finze, Maik
T1  - Dismutation of Tricyanoboryllead Compounds: The Homoleptic Tetrakis(tricyanoboryl)plumbate Tetraanion
JF  - Angewandte Chemie
N2  - A series of unprecedently air-stable (tricyanoboryl)plumbate anions was obtained by the reaction of the boron-centered nucleophile B(CN)\(_{3}\)\(^{2-}\) with triorganyllead halides. Salts of the anions [R\(_{3}\)PbB(CN)\(_{3}\)]\(^{-}\) (R=Ph, Et) were isolated and found to be stable in air at room temperature. In the case of Me\(_{3}\)PbHal (Hal=Cl, Br), a mixture of the anions [Me\(_{4-n}\)Pb{B(CN)\(_{3}\)}\(_{n}\)]\(^{n-}\) (n=1, 2) was obtained. The [Et\(_{3}\)PbB(CN)\(_{3}\)]− ion undergoes stepwise dismutation in aqueous solution to yield the plumbate anions [Et4\(_{4-n}\)Pb{B(CN)\(_{3}\)}\(_{n}\)]\(^{n-}\) (n=1–4) and PbEt\(_{4}\) as by-product. The reaction rate increases with decreasing pH value of the aqueous solution or by bubbling O\(_{2}\) through the reaction mixture. Adjustment of the conditions allowed the selective formation and isolation of salts of all anions of the series [Et\(_{4-n}\)Pb{B(CN)\(_{3}\)}\(_{n}\)]\(^{n-}\) (n=2–4) including the homoleptic tetraanion [Pb{B(CN)\(_{3}\)}\(_{4}\)]\(^{4-}\).
KW  - anions
KW  - boron
KW  - cyanoborates
KW  - dismutations
KW  - lead
Y1  - 2022
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-318257
VL  - 61
IS  - 24
ER  - 
TY  - JOUR
A1  - He, Jiang
A1  - Rauch, Florian
A1  - Friedrich, Alexandra
A1  - Sieh, Daniel
A1  - Ribbeck, Tatjana
A1  - Krummenacher, Ivo
A1  - Braunschweig, Holger
A1  - Finze, Maik
A1  - Marder, Todd  B.
T1  - N-Heterocyclic Olefins as Electron Donors in Combination with Triarylborane Acceptors: Synthesis, Optical and Electronic Properties of D-π-A Compounds
JF  - Chemistry - A European Journal
N2  - N‐heterocyclic olefins (NHOs), relatives of N‐heterocyclic carbenes (NHCs), exhibit high nucleophilicity and soft Lewis basic character. To investigate their π‐electron donating ability, NHOs were attached to triarylborane π‐acceptors (A) giving donor (D)–π–A compounds 1–3. In addition, an enamine π‐donor analogue (4) was synthesized for comparison. UV–visible absorption studies show a larger red shift for the NHO‐containing boranes than for the enamine analogue, a relative of cyclic (alkyl)(amino) carbenes (CAACs). Solvent‐dependent emission studies indicate that 1–4 have moderate intramolecular charge‐transfer (ICT) behavior. Electrochemical investigations reveal that the NHO‐containing boranes have extremely low reversible oxidation potentials (e.g., for 3, \(E^{ox}_{1/2}\) =−0.40 V vs. ferrocene/ferrocenium, Fc/Fc\(^+\), in THF). Time‐dependent (TD) DFT calculations show that the HOMOs of 1–3 are much more destabilized than that of the enamine‐containing 4, which confirms the stronger donating ability of NHOs.
KW  - donor-acceptor systems
KW  - electrochemistry
KW  - photophysical prosperties
KW  - N-heterocyclic olefins
KW  - triarylboranes
Y1  - 2019
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-204690
VL  - 25
ER  -