TY - JOUR

T1 - Cationic Chains of Parent Arsanylboranes and Substituted Phosphanylboranes

AU - Marquardt, Christian

AU - Balázs, Gábor

AU - Baumann, Josef

AU - Virovets, Alexander V.

AU - Scheer, Manfred

PY - 2017/8/22

Y1 - 2017/8/22

N2 - The substituted monomeric phosphanylboranes Ph2P−BH2⋅NMe3 (1) and tBuHP−BH2⋅NMe3 (2) have been used for the synthesis of cationic chain compounds built up by R2P−BH2 units. With a simple synthesis route, the highly stable cations [Me3N⋅H2B−PR1R2−BH2⋅NMe3]+ (1 a, 2 a) and [Me3N⋅H2B−PR1R2−BH2−PR1R2−BH2⋅NMe3]+ (1 b, 2 b) (R1=R2=Ph; R1=H, R2=tBu) are obtained as iodide (I−) salts. The reaction of H2As−BH2⋅NMe3 (3) with IBH2⋅SMe2 leads to [Me3N⋅H2B−AsH2−BH2−AsH2−BH2⋅NMe3][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(BH2⋅NMe3)(CMe=NH)2(BH2)}][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.

AB - The substituted monomeric phosphanylboranes Ph2P−BH2⋅NMe3 (1) and tBuHP−BH2⋅NMe3 (2) have been used for the synthesis of cationic chain compounds built up by R2P−BH2 units. With a simple synthesis route, the highly stable cations [Me3N⋅H2B−PR1R2−BH2⋅NMe3]+ (1 a, 2 a) and [Me3N⋅H2B−PR1R2−BH2−PR1R2−BH2⋅NMe3]+ (1 b, 2 b) (R1=R2=Ph; R1=H, R2=tBu) are obtained as iodide (I−) salts. The reaction of H2As−BH2⋅NMe3 (3) with IBH2⋅SMe2 leads to [Me3N⋅H2B−AsH2−BH2−AsH2−BH2⋅NMe3][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(BH2⋅NMe3)(CMe=NH)2(BH2)}][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.

KW - arsenic

KW - boron

KW - cationic chains

KW - phosphorus

KW - pnictogenylboranes

KW - PHOSPHORUS

KW - PHOSPHANES

KW - COMPLEXES

KW - BORANE

KW - DICATIONS

KW - SALTS

KW - CONVENIENT ROUTE

KW - BONDS

KW - CHEMISTRY

KW - DERIVATIVES

UR - http://www.scopus.com/inward/record.url?scp=85026477104&partnerID=8YFLogxK

U2 - 10.1002/chem.201702384

DO - 10.1002/chem.201702384

M3 - Article

AN - SCOPUS:85026477104

VL - 23

SP - 11423

EP - 11429

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 47

ER -