Beiträge zur Chemie des Phosphors. 59. Zur Synthese und Struktur von (C₆H₅PS)₃

Abstract

1,2,4‐Triphenyl‐1‐thio‐cyclo‐3,5‐dithia‐1,2,4‐triphosphan (C6H5PS)3 (1) wird durch Reaktion von Dikalium‐triphenyl‐triphosphid (4) mit Dichlortrisulfan sowie durch Umsetzung von Phenylphosphin mit Schwefeldichlorid in sehr guter Ausbeute erhalten. Außerdem bildet sich 1 – zusammen mit dem Cyclo‐thia‐phosphan (C6H5P)4 (3) – bei der Umsetzung von 1,2‐Diphenyl‐1,2‐dihalogen‐diphosphanen mit Schwefelwasserstoff oder Disulfan sowie aus 4 und Dischwefeldichlorid. – Die Gesamtheit der spektroskopischen Befunde, insbesondere das 31P‐Kernresonanzspektrum, ergibt für 1 eindeutig die Heterocyclophosphan‐Struktur V mit fünfgliedrigem P3S2‐Ring, in dem die S‐Atome isoliert stehen und eines der direkt miteinander verbundenen P‐Atome außer der Phenylgruppe noch ein exoständiges S‐Atom trägt.

Phosphorus-Chalcogen Ring Expansion and Metal Coordination

“…The solid-state structures of 2Ch resemble those previously reported. 23,25,26 data is similar to that found for 2S. The same is true also for P-Ch bond distances in 7SCu, 7SAg, and 2S: 2.1334(16), 2.128(2) and 2.1393(2) Å, respectively.…”

“…19,20 While there have been extensive studies on P(V)-Ch derivatives, examples of P(III) within the ring core are more uncommon, especially in regards to those with a general formula (RPCh)n. Examples of (RPCh)n have been reported for n = 2, 3, and 4, where bulky R groups are required to kinetically stabilize the P(III) centre ( Figure 1, B-D). [21][22][23][24][25][26] In particular, our group has recently reported the syntheses of strained (RPCh)2 rings 1Ch (Ch = S, Se) with P in the +3 oxidation state, the first representatives of these strained compounds, by installing m-terphenyl substituents at phosphorus. 24 Although select examples of (RPCh)n have been reported since the early 1980's, a thorough examination of their chemistry has not been published, though related P(III)-Ch-N macrocycles have been reported to form polynuclear Ag(I) sandwich complexes upon reaction with various amounts of AgOTf (Figure 1, E).…”

The preparation and characterization of binary phosphorus–selenium rings

“…The "P NMR is second order, even at 101.4 MHz. The pattern is similar to that given by the tetraphospholanes [20-231. When (PhP)5 and sulphur are reacted together such that the P:S ratio is 1 : 1, (PhPS), is produced [22]. When a 1 : 1 PhP: Se ratio is refluxed in toluene for 2 h, the 31P NMR spectrum reveals the presence of 3 together with 5.…”

“…was used as received. (PhP)5 [15] and (PhPS)3 [4] were prepared by literature methods. Li2Se was prepared by an adaptation of a published method [16].…”

Recent advances in organophosphorus–chalcogen and organophosphorus–pincer based macrocyclic compounds and their metal complexes

“…In the recent past, phosphinidene chalcogenides (R-PvE) have been employed in transition metal chemistry, [82][83][84] cycloaddition reactions, designing many unique phosphine ligands, 85,86 and also in the construction of larger [RPE] n rings (D and E, Chart 1). [87][88][89] Although numerous examples of the type [RPE] 2 (C, Chart 1) with pentavalent phosphorus atoms are known, 64,90,91 the series of the type [RPE] 2 with trivalent phosphorus atoms is unstable and less extensive. Mechanistic investigations using density functional theory (DFT) calculations suggested that the P III centers in C (Chart 1) can exhibit a Lewis acidic character and often readily react with strong nucleophiles like NHCs and cleave the four-membered ring by trapping the monomers Ar*-PvS and Ar*-PvSe.…”