A Persistent Phosphanyl‐Substituted Thioketyl Radical Anion

Abstract

Alkali metalsalts, M + [Ter(iPr)PÀ C(=S)À P(iPr) 2 S] *À (M = Na, K; 2_M; Ter = 2,4,phenyl) containing a room-temperature-stable thioketyl radical anion were obtained by reduction of the thioketone precursor, Ter(iPr)PÀ C(=S)À P(iPr) 2 S (1), with alkali metals (Na, K). Single-crystal X-ray studies as well as EPR spectroscopy revealed the unequivocal existence of a thioketyl radical anion in the solid state and in solution, respectively. The computed Mulliken spin density within 2_M is mainly located at the sulfur (49 %) and the carbonyl carbon (33 %) atoms. Upon adding [2.2.2]-cryptand to the radical species 2_K to minimize the interionic interaction, an activation reaction was observed, yielding a potassium salt with a phosphanyl thioether based anion, [K(crypt)] + [Ter(iPr)PÀ C(À S-iPr)À P(iPr) 2 S] À (3) as the product of an intermolecular shift of an iPr group from a second anion. The products were fully characterized and application of the radical anion as a reducing agent was demonstrated.

Synthesis of Stable Potassium Phosphinophosphides and Reaction with Organosilyl Halides and Chlorophosphanes

“…The molecular structures of both 5a and 5b in the solid state show coordination of the K + ion by the P1 atom ( 5a , K1···P1 = 3.2578(4) Å; 5b , K1···P1 = 3.2711(8) Å; ∑ r vdW (K···P) = 4.55 Å). The K + ion in 5a and 5b is furthermore coordinated via the Mes group of the Ter substituent [average K1···C distance in 5a = 3.31 Å; average K1···C distance in 5b = 3.39 Å; ∑ r vdW (K···C) = 4.45 Å], which displays a common structural motif in Ter-stabilized potassium phosphides. ,, Additionally, two molecules of DME coordinate the K + ion in both 5a and 5b . Upon deprotonation, the R 1 –P2–R 1 angle remains approximately constant [C i Pr –P2–C i Pr : 4a , 104.60(7)°; 5a , 104.64(6)°; C Ph –P2–C Ph : 4b , 100.66(11)°; 5b , 97.54(9)°].…”

Trendbericht Anorganische Chemie 2023: Hauptgruppen

“…39) Anorganische (ionische) Ozonoide mit Natrium oder Kalium darstellen. 42) Andrews, De Backere und Stephan haben aus SOCl 2 und Me-SiO 3 SCF 3 hochreaktive SO 2+ -Ionen synthetisiert. Diese Dikationen lassen sich durch pyridinartige Liganden stabilisieren und als Salze isolieren.…”

A cyclic thioketone as biradical heterocyclopentane-1,3-diyl: synthesis, structure and activation chemistry

“…For example, activation of CO with diphosphadiazanediyl 1 already occurs at room temperature (1 bar). However, unlike alkynes, which insert with both carbon atoms into the P 2 N 2 ring of the [2.1.1]bicycle (species 2R) to form a [3.1.0]bicycle (3R) with a transannular P-P bond, 13,14 CO exhibits carbene-analogous reactivity, so that only the C atom of species 4O is inserted into a P-N bond, resulting in the formation of a formal cyclic ketone (5O), in which the biradical character is retained. 11 This biradical cyclic ketone (as well as the analogous isonitrile reaction products 5NR′) can be regarded as a stable cyclopentane-1,3-diyl analogue (ca.…”

“…[32][33][34][35][36] The isolation of stable thioketones (with respect to oligomerization) 37 as well as thioaldehydes can be achieved via kinetic stabilization by introducing spatially demanding substituents. 14,38 Substitution of the oxygen atom by a sulphur atom in a ketone leads to the formal formation of a thioketone and therefore to significant changes in the chemical reactivity as well as stability of the CvX carbon-chalcogen double bond (X = O, S). Firstly, the polarity of the bond changes (cf.…”

“…32–36 The isolation of stable thioketones (with respect to oligomerization) 37 as well as thioaldehydes can be achieved via kinetic stabilization by introducing spatially demanding substituents. 14,38…”