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Anionic Chains of Parent Pnictogenylboranes
Author(s) -
Marquardt Christian,
Kahoun Tobias,
Stauber Andreas,
Balázs Gábor,
Bodensteiner Michael,
Timoshkin Alexey Y.,
Scheer Manfred
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201608875
Subject(s) - chemistry , pnictogen , nucleophile , boron , nuclear magnetic resonance spectroscopy , medicinal chemistry , mass spectrometry , infrared spectroscopy , stereochemistry , spectroscopy , crystallography , organic chemistry , physics , superconductivity , chromatography , quantum mechanics , catalysis
We report on the synthesis and structural characterization of unprecedented anionic parent compounds of mixed Group 13/15 elements. The reactions of the pnictogenylboranes H 2 E‐BH 2 ⋅NMe 3 ( 1 a =P, 1 b =As) with phosphorus and arsenic centered nucleophiles of the type [EH 2 ] − (E=P, As) lead to the formation of compounds of the type [H 2 E‐BH 2 ‐E′H 2 ] − ( 2 : E=E′=P; 3 : E=E′=As; 4 : E=P, E′=As) containing anionic pnictogen–boron chain‐like units. Furthermore, a longer 5‐membered chain species [H 2 As‐BH 2 ‐PH 2 ‐BH 2 ‐AsH 2 ] − ( 5 ) and a cyclic compound [NHC dipp ‐H 2 B‐PH 2 ‐BH 2 ‐NHC dipp ] + [P 5 B 5 H 19 ] − ( 6 ) containing a n ‐butylcyclohexane‐like anion were obtained. All the compounds have been characterized by X‐ray structure analysis, multinuclear NMR spectroscopy, IR spectroscopy, and mass spectrometry. DFT calculations elucidate their high thermodynamic stability, the charge distribution, and give insight into the reaction pathway.