Institut für Anorganische Chemie, Universität Regensburg, 93053, Regensburg, Germany.
Institute of Chemistry, Saint Petersburg State University, Universitetskaya emb., Sankt-Peterburg, 7/9, 199304 St. Petersburg, Russia.
Chemistry. 2023 Jan 18;29(4):e202202911. doi: 10.1002/chem.202202911. Epub 2022 Nov 29.
The coordination chemistry of only Lewis-base (LB)-stabilized pnictogenylboranes EH BH ⋅NMe (E=P, As) towards Tl(I) salts has been studied. The reaction of Tl[BAr ] (BAr =[B(3,5-C H Cl ) ] ) with the corresponding pnictogenylborane results in the formation of [Tl(EH BH ⋅NMe )][BAr ] (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 EH BH ⋅ NMe in [Tl(EH BH ⋅ NMe ) ][WCA] (2 a: E=P, WCA=TEF ; 2 b: E=As, WCA=TEF) (TEF=[Al{OC(CF ) } ] , TEF =[Al{(OC(CF ) (CCl )} ] ). Furthermore, by using two equivalents of PH BH ⋅NMe , a Tl(I)-mediated P-P coupling takes place in CH Cl as solvent resulting in [Me N⋅BH PH PHBH ⋅NMe ][WCA] (WCA=TEF, 3 a; BAr , 3 b; TEF , 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.
我们研究了仅路易斯碱（LB）稳定的磷杂硼烷 EH BH ⋅NMe（E=P，As）与 Tl（I）盐的配位化学。Tl[BAr ]（BAr =[B(3,5-C H Cl ) ]）与相应的磷杂硼烷反应生成[Tl(EH BH ⋅NMe )][BAr ]（1a：E=P；1b：E=As）。虽然 1a/b 中的 Tl 离子是单核配位的，但 Tl（I）盐中弱配位阴离子（WCA）的交换导致 Tl 原子通过 EH BH ⋅NMe 的三个当量配位形成三角锥形配位模式，形成[Tl(EH BH ⋅NMe ) ][WCA]（2a：E=P，WCA=TEF；2b：E=As，WCA=TEF）（TEF=[Al{OC(CF ) } ]，TEF=[Al{(OC(CF ) (CCl )} ]）。此外，在 CH Cl 溶剂中，使用两当量的 PH BH ⋅NMe，发生 Tl（I）介导的 P-P 偶联反应，生成[Me N⋅BH PH PHBH ⋅NMe ][WCA]（WCA=TEF，3a；BAr，3b；TEF，3c）。相比之下，对于砷衍生物 1b 和 2b，没有观察到偶联反应。通过量子化学计算阐明了潜在的化学过程。
