Alkali Metal Thioselenophosphinates, M[SeSPR2]: One-Pot Multicomponent Synthesis, DFT Study, and Synthetic Application

作者：Artem'ev Alexander V; Gusarova Nina K; Bagryanskaya Irina Yu; Doronina Evgeniya P; Verkhoturova Svetlana I; Sidorkin Valery F; Trofimov Boris A^*

来源：European Journal of Inorganic Chemistry, 2013, 2013(3): 415-426.

DOI：10.1002/ejic.201200947

• Sulfur
• Selenium
• Phosphanes
• Multicomponent reactions
• Solid-state structures

Diverse alkali metal thioselenophosphinates, M[SeSPR2] (M = Li, Na, K, Rb, and Cs; R = alkyl, aryl, aralkyl, and hetaralkyl), have been synthesized in 78-94% yields by means of a one-pot multicomponent reaction between secondary phosphanes, sulfur, selenium, and alkali metal hydroxides under mild conditions (room temperature, -50 degrees C, 0.5 h, EtOH). The molecular and electronic structure of the [SeSPPh2](-) anion and its coordination behavior towards Li+, Na+, and K+ cations have been investigated at the B3LYP level of theory. The alkylation of the alkali metal thioselenophosphinates with various organic halides proceeds regiosecifically at the selenium center to form Se-organyl thioselenophosphinates, R2P(S) SeR' (R' = Me, Et, Bn, allyl, propargyl), in 78-96% yields. By the action of molecular iodine, the alkali metal thioselenophosphinates instantly (room temperature, ca. 1 s, 1,4-dioxane) undergo selective Se-Se oxidative coupling to afford the corresponding diselenides, R2P(S) SeSe(S)PR2, in 81-92% yields. The alkali metal thioselenophosphinates are readily converted into the corresponding ammonium derivatives. Square-planar Ni-II complexes, Ni[SeSPR2](2) (R = Ph, CH2CH2Ph), have been prepared in 68-81% yield by the treatment of sodium thioselenophosphinates, Na[SeSPR2], with NiBr2 at room temperature (EtOH/CH2Cl2, 10 min).

• 出版日期2013-1