Premium
Cationic Chains of Parent Arsanylboranes and Substituted Phosphanylboranes
Author(s) -
Marquardt Christian,
Balázs Gábor,
Baumann Josef,
Virovets Alexander V.,
Scheer Manfred
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201702384
Subject(s) - cationic polymerization , chemistry , iodide , acetonitrile , monomer , nuclear magnetic resonance spectroscopy , stereochemistry , mass spectrometry , medicinal chemistry , crystallography , polymer chemistry , organic chemistry , polymer , chromatography
The substituted monomeric phosphanylboranes Ph 2 P−BH 2 ⋅ NMe 3 ( 1 ) and t BuHP−BH 2 ⋅ NMe 3 ( 2 ) have been used for the synthesis of cationic chain compounds built up by R 2 P−BH 2 units. With a simple synthesis route, the highly stable cations [Me 3 N ⋅ H 2 B−PR 1 R 2 −BH 2 ⋅ NMe 3 ] + ( 1 a , 2 a ) and [Me 3 N ⋅ H 2 B−PR 1 R 2 −BH 2 −PR 1 R 2 −BH 2 ⋅ NMe 3 ] + ( 1 b , 2 b ) (R 1 =R 2 =Ph; R 1 =H, R 2 = t Bu) are obtained as iodide (I − ) salts. The reaction of H 2 As−BH 2 ⋅ NMe 3 ( 3 ) with IBH 2 ⋅ SMe 2 leads to [Me 3 N ⋅ H 2 B−AsH 2 −BH 2 −AsH 2 −BH 2 ⋅ NMe 3 ][I] ( 3 a ), the longest so far known arsanylborane chain. Compound 3 a reacts with acetonitrile through a formal hydroarsination reaction to form [cyclo‐{As(BH 2 ⋅ NMe 3 )(CMe=NH) 2 (BH 2 )}][I] ( 4 ). The reported synthetic strategy has proved to be a powerful tool for the formation of small, cationic oligomeric units. All products were comprehensively characterized by X‐ray structure analysis, NMR, IR spectroscopy, and mass spectrometry in cooperation with DFT calculations.