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  - Zapf, Ludwig
A1  - Peters, Sven
A1  - Bertermann, Rüdiger
A1  - Radius, Udo
A1  - Finze, Maik
T1  - Tricyanoborane‐Functionalized Anionic N‐Heterocyclic Carbenes: Adjustment of Charge and Stereo‐Electronic Properties
JF  - Chemistry – A European Journal
N2  - The 1‐methyl‐3‐(tricyanoborane)imidazolin‐2‐ylidenate anion (2) was obtained in high yield by deprotonation of the B(CN)3‐methylimidazole adduct 1. Regarding charge and stereo‐electronic properties, anion 2 closes the gap between well‐known neutral NHCs and the ditopic dianionic NHC, the 1,3‐bis(tricyanoborane)imidazolin‐2‐ylidenate dianion (IIb). The influence of the number of N‐bonded tricyanoborane moieties on the σ‐donating and π‐accepting properties of NHCs was assessed by quantum chemical calculations and verified by experimental data on 2, IIb, and 1,3‐dimethylimidazolin‐2‐ylidene (IMe, IIa). Therefore NHC 2, which acts as a ditopic ligand via the carbene center and the cyano groups, was reacted with alkyl iodides, selenium, and [Ni(CO)\(_{4}\)] yielding alkylated imidazoles 3 and 4, the anionic selenium adduct 5, and the anionic nickel tricarbonyl complex 8, respectively. The results of this study prove that charge, number of coordination sites, buried volume (%V\(_{bur}\)) and σ‐donor and π‐acceptor abilities of NHCs can be effectively fine‐tuned via the number of tricyanoborane substituents.
KW  - N-heterocyclic carbene
KW  - anionic carbene
KW  - boron
KW  - cyanoborate
KW  - imidazolate
Y1  - 2022
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-287200
VL  - 28
IS  - 39
ER  -