FRC Kazan Scientific Center of RAS, Arbuzov Institute of Organic and Physical Chemistry, Arbuzov Str. 8, 420088 Kazan, Russia.
Department of Organic Chemistry, Kazan Federal University, Kremlyovskaya Str. 18, 420008 Kazan, Russia.
Molecules. 2021 Jan 21;26(3):538. doi: 10.3390/molecules26030538.
Reaction of heterometallic cubane-type cluster complexes-[Mo{Pd(dba)}SCl(dbbpy)]PF, [Mo{Pd(tu)}SCl(dbbpy)]Cl and [Mo{Pd(dba)}S(acac)(py)]PF, where dba-dibenzylideneacetone, dbbpy-4,4'-di--butyl-2,2'-bipyridine, tu-thiourea, acac-acetylacetonate, py-pyridine, with white phosphorus (P) in the presence of water leads to the formation of phosphorous acid HPO as the major product. The crucial role of the Pd atom in the cluster core {MoPdS} has been established in the hydrolytic activation of P molecule. The main intermediate of the process, the cluster complex [Mo{PdP(OH)}SCl(dbbpy)] with coordinated P(OH) molecule and phosphine PH, have been detected by P NMR spectroscopy in the reaction mixture.
异金属笼型簇合物-[Mo{Pd(dba)}SCl(dbbpy)]PF、[Mo{Pd(tu)}SCl(dbbpy)]Cl 和 [Mo{Pd(dba)}S(acac)(py)]PF 与三苯基膦(P)在水中的反应导致形成主要产物亚磷酸 HPO。在 P 分子的水解活化中,簇核{MoPdS}中的 Pd 原子发挥了关键作用。通过 P NMR 光谱在反应混合物中检测到该过程的主要中间体,即具有配位 P(OH)分子和膦 PH 的簇合物 [Mo{PdP(OH)}SCl(dbbpy)]。