Coordination of Pnictogenylboranes Towards Tl(I) Salts and a Tl- Mediated P-P Coupling.
Chemistry
; 29(4): e202202911, 2023 Jan 18.
Article
em En
| MEDLINE
| ID: mdl-36259382
ABSTRACT
The coordination chemistry of only Lewis-base (LB)-stabilized pnictogenylboranes EH2 BH2 â
NMe3 (E=P, As) towards Tl(I) salts has been studied. The reaction of Tl[BArCl ] (BArCl =[B(3,5-C6 H3 Cl2 )4 ]- ) with the corresponding pnictogenylborane results in the formation of [Tl(EH2 BH2 â
NMe3 )][BArCl ] (1 a E=P; 1 b E=As). Whereas the Tl ion in 1 a/b is monocoordinated, the exchange of the weakly coordinating anion (WCA) in the Tl(I) salt leads to the formation of a trigonal pyramidal coordination mode at the Tl atom by coordination of three equivalents of EH2 BH2 â
NMe3 in [Tl(EH2 BH2 â
NMe3 )3 ][WCA] (2 a E=P, WCA=TEFCl ; 2 b E=As, WCA=TEF) (TEF=[Al{OC(CF3 )3 }4 ]- , TEFCl =[Al{(OC(CF3 )2 (CCl3 )}4 ]- ). Furthermore, by using two equivalents of PH2 BH2 â
NMe3 , a Tl(I)-mediated P-P coupling takes place in CH2 Cl2 as solvent resulting in [Me3 Nâ
BH2 PH2 PHBH2 â
NMe3 ][WCA] (WCA=TEF, 3 a; BArCl , 3 b; TEFCl , 3 c). In contrast, for the arsenic derivatives 1 b and 2 b, no coupling reaction is observed. The underlying chemical processes are elucidated by quantum chemical computations.
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MEDLINE
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En
Ano de publicação:
2023
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Article