The Hexaphosphapentaprismane P6C4tBu4: A “Jaws-Like” Cage Molecule That Bites!

Opening “Jaws”: Functionalisation of the hexaphosphapentaprismane cage, P6C4Bu4, affording X2P6C4Bu4 (X = Me, I), crystal and molecular structures of X2P6C4Bu4 (X = Me, I) and [cis-PtCl2Me2P6C4Bu4]

“…In view of the ease and specificity of these insertion reactions we have likened this behaviour to that of the well-known shark ''Jaws" of movie fame [4,5]. Also noteworthy is the quantitative insertion into 1 of the isolobal zerovalent platinum fragment [Pt(PPh 3 ) 2 ], even though there are no fewer than six phosphorus lone pairs available for simple r-complexation to the metal [6] (Scheme 1).…”

“…Subsequently we reported a more convenient synthetic route involving ambient temperature oxidative coupling of two P 3 C 2 t Bu 2 anions by I 2 [2 (o)]. The hexaphosphapentaprismane cage 1 is unusual in that it readily undergoes a variety of ambient temperature insertion reactions specifically and quantitatively into the unique P-P bond linking the two 5-membered rings [4,5]. Thus, treatment with the chalcogens, E, (E = S, Se or Te), readily afforded the new cages shown in Scheme 1.…”

“…An understanding as to why the unique P-P bond of 1 is the most reactive site in 1, came from quantum chemical calculations carried out at the B3LYP/6-316G * level of theory on the hypothetical parent hexaphosphapentaprismane, P 6 C 4 H 4 [4], which revealed that both the HOMO and LUMO of the cage were concentrated at this particular P-P bond. In view of the ease and specificity of these insertion reactions we have likened this behaviour to that of the well-known shark ''Jaws" of movie fame [4,5].…”

Phosphorus‐Selenium Heterocycles from the Tetraphospholane (PhP)4CH2

“…[16Ϫ18] The first example (10, Figure 3), prepared by insertion of Se into a cage phosphane does not offer many structural similarities due to its rigid cage structure. [16] The second known compound containing the PPCPSe ring sequence (11, Figure 3) was prepared by the action of carbon disulfide on the product of the reaction of lithium selenide (obtained from LiHBEt 3 and Se) with phenyl dichlorophosphane. [18] Interestingly, the substitution pattern as well as the configuration of substituents in 11 is nearly identical to those in 7a Ϫ the P atoms directly bonded to the C atom bear exocyclic Se atoms and the configuration of Ph substituents on two neighbouring P atoms is trans.…”

Hexaphosphapentaprismane: A New Gateway to Organophosphorus Cage Compound Chemistry

“…[23] A single-crystal X-ray diffraction study reveals the remarkable structure of 11 in the solid state ( Figure 4, Table 4, and Table 6), which consists of three HgC 4 tBu 4 P 6 units; each unit is linked to the other two by coordinative bonds from phosphorus lone pairs.…”