Diphospholyl and triphospholyl zirconium π-complexes: Ziegler–Natta oligomerization catalysts and reactive intermediates in P–C cage formation by hydrolysis

The “Hidden” Reductive [2+2+1]‐Cycloaddition Chemistry of 2‐Phosphaethynolate Revealed by Reduction of a Th‐OCP Linkage

“…Although examples of [2+2+1] cycloaddition have been proposed in group 14‐OCP systems to produce a similar [O 2 (C 2 P 3 )] 3− , [16] it has not yet been observed in actinide‐ or transition metal‐OCP chemistry nor in a reductive scenario. Importantly, thermolysis of 5 in C 6 D 6 at 80 °C (Figure S17) gives 6 and 4 , with the presumed phosphorus‐dicyclopentadiene‐type species (H 6 C 4 P 6 ) as the by‐product, [24] confirming 5 as an intermediate to 6 . We suggest that intermediate 5 can be isolated at all and then converted to 6 in a tractable manner is due to the bulky [Th(Tren TIPS )O] − unit acting as a protecting then leaving group to modulate the kinetics the of these reactions.…”

Nitrogen, phosphorus, arsenic, antimony and bismuth

“…Related di-and triphospholide zirconium complexes have also been reported and an important feature is that it is possible to hydrolytically remove the phosphorus-containing groups to reveal a number of saturated and unsaturated phosphorus clusters. 61 The reaction of the ''Jaws'' hexaphosphorus cage P 6 C 4 t Bu 4 , 58, with iodine results in P-P bond cleavage to afford I 2 P 6 C 4 t Bu 4 , 59. 62 Reaction of the iodo-substituted complex with LiMe results in the formation of Me 2 P 6 C 4 t Bu 4 , 60.…”

Access to Phosphorus‐Rich Zirconium Complexes

“…A similar behavior with an inequivalence of the protons of the Cp R ring is observed in [{h 5 -P 2 (CtBu) 3 }CpZrCl 2 ] as well as in [{h 5 -P 3 (CtBu) 2 }CpZrCl 2 ]. [18] The 31 P{ 1 H} NMR spectrum of 3 shows a higher-order spectrum that could be simulated as an AA'MM'XY spin system. [16] The main feature of the molecular structure of 3 is a ZrP 6 C 2 core, which displays a cuneane-like structural motif (Figure 1).…”