2,4-Diferrocenyl-1,3-dithiadiphosphetane 2,4-disulfide; structure and reactions with catechols and [PtCl2(PR3)2](R = Et or Bun)

One‐Pot Approach to Organo‐Phosphorus–Chalcogen Macrocycles Incorporating Double OP(S)SCn or OP(Se)SeCn Scaffolds: A Synthetic and Structural Study

“…[15] We envisagedt hat this method hast he potential to provide extremely efficient access to ar ange of macrocycles bearing double OÀP(S)ÀSÀC n or OÀP(Se)ÀSeÀC n scaffolds because the combinatorial variation of scaffold elements can lead to the generation of aunique scaffold from each macrocyclization process. The three reagents utilised to accomplish the one-pot three-component reaction are:Lawesson'sreagent (LR), whichi sc ommerciallya vailable;aferrocene analogue of Lawesson'sr eagent, 2,4-diferrocenyl-1,3,2,4-diathiadiphosphetane 2,4-disulfide [FcP(m-S)S] 2 (FcLR)-the preparation, spectroscopic characterisation and crystal structure of FcLR has been reportedb yo ur group; [16,17] and Woollins' reagent (WR). [12m] First, treating FcLR with an equimolar amount of disodium alkane-bis(olate)s, which were obtained from dialcohols and NaH, delivered the disodium bis(phenylphosphonodiselenoate)s, the latter were in situ converted into the corresponding nine-to fifteen-membered phosphorus-sulfur heterocycles 1-15 in moderate-to-excellent yields (43 to 92 %) by further treatment with an equimolar amount of various nucleophilic reagents,f or instance, dibromides as depictedi nS cheme 1 and Ta ble 1.…”

“…Single-crystal X-ray structures of 3 (SR isomer; hydrogen atoms are omitted for clarity). Selectedb ond lengths [] and angles [8]: S(1)ÀP(1) 2.093(4), S(2)ÀP(2) 2.088(4), S(3)ÀP(1) 1.935(4),S (4)ÀP(2) 1.928(4), P(1)ÀO(1) 1.605 (7), P(2)ÀO(2) 1.599(6);S (1)-P(1)-S(3) 114.50 (17), S(2)-P(2)-S(4) 108.04 (16) [8]: S(1)ÀP(1) 2.098(4), S(2)ÀP(2) 2.091(4), S(3)ÀP(1) 1.931(4),S (4)ÀP(2) 1.933(4), P(1)ÀO(1) 1.592 (7), P(2)ÀO(2) 1.601 (7);S (1)-P(1)-S(3) 107.70 (16), S(2)-P(2)-S(4) 107.69 (16) The structures of 10 and 11,a sd epicted in Figure 5a nd Figure 6, consist of similarf rameworks. The thirteen-and fourteen-membered rings are also highly creased with two outside ferrocenyl rings lying in the same direction of the cavity and being above the plane defined by the two phosphorus and two oxygen atoms; meanwhile two exocyclic sulfur atoms which are directly attached to phosphorusc entresa re crinkled in a trans-orientation.…”

“…Single-crystal X-ray structures of 10 (SR isomer;hydrogen atoms are omitted for clarity). Selected bond lengths [] and angles [8]: S(1)ÀP(1) 2.083(2), S(2)ÀP(2) 2.077(2), S(3)ÀP(1) 1.929(3), S(4)ÀP(2) 1.926(3), P(1)ÀO(1) 1.608(4), P(2)ÀO(2) 1.621(4);S (1)-P(1)-S(3) 117.65(9), S(2)-P(2)-S(4) 107.45(10), S(1)-P(1)-O(1) 99.13 (16), S(2)-P(2)-O(2) 106.37 (15), S(3)-P(1)-O(1) 112.67 (17), S(4)-P(2)-O(2) 117.31 (17). Figure 6.…”

Application of four-membered ring chalcogenation reagents to the synthesis of new phosphorus-chalcogen heterocycles

“…In the newly formed ring the central phosphorus atom lies 0.195 Å in 1, 0.349 Å in 2 and 0.332 Å in 3 out of the P-S-S-C n (n = 2, 3) mean plane. The P=S double bond lengths in the structures of 1-3 are 1.934(2) Å, 1.9390(10) Å and 1.9351(7) Å, respectively, cf dithiophosphono disulfides [1.9203(14) -1.9303(7) Å], [29][30][31] are slightly shorter than that in other terminal phosphine sulphide bond lengths in the Cambridge Crystallographic Database (average 1.965 Å). The reaction of WR and alkyl-or aryl-dithiol was carried out under identical condition.…”

“…Analogous reactions were carried out by using FcLR 29,30 and dithiols. The reaction of FcLR with two molar equivalents of alkyl-or aryl-dithiols in refluxing toluene afforded five or seven-membered ring heterocycles 8-10 in good yields as shown in Scheme 2.…”