Bis(η⁵‐cyclopentadienyl)‐1,3‐diphosphabicyclo[1.1.0]butane‐2,4‐diylzirconium: A Simple Synthesis of an Unusual Molecule

Abstract

The metal‐substituted diphosphabicyclobutane 1 and not the expected metalladiphosphacyclopentadiene was formed in the reaction shown below. The distances show unequivocally that a PP bond but no ZrP bond is present in 1. The tBu groups are arranged in a nearly eclipsed fashion.

Nucleophilic substitution reactions of the tricyclic triphosphorus cage P3(CBut)2: a novel route to polyphosphorus phosphenium complexes

“…Few X-ray structures of compounds containing the tricyclic cage or related species are known, indeed to the best of our knowledge, only I(P 1 )-P 3 (CBu t ) 2 7, 7 and Zr(g 5 -C 5 H 5 ) 2 {P 2 (CBu t ) 2 } 2, 14 have been reported, therefore the structure of the tricylic cage is worthy of comment. A common feature of all of these compounds is the short P 2 -P 3 distance.…”

Zirconium - Phosphorus Chemistry: Strategies in Syntheses, Reactivity, Catalysis, and Utility

“…[86] Structural characterization revealed the novel bicyclic structure. Binger also described the isolation of 76 and its subsequent reaction with BEt 3 to give the trimeric species 77.…”

Multiple bonding versus cage formation in organophosphorus compounds: the gas-phase structures of tricyclo-P3(CBut)2Cl and PC–But determined by electron diffraction and computational methods

“…Compound 1 is itself prepared by the reaction of Zr(h 5 -C 5 H 5 ) 2 [P 2 (CBu t ) 2 ] with PCl 3 . 3 We have used this molecule as a starting point for several diverse studies and have shown that it provides an atom-efficient route to and AE¢ reaction pathways, the latter being a previously unseen substitution pathway in phosphorus chemistry. 6,7 In order to rationalise these observations fully it was clear that knowledge of the precise topology of 1 was required.…”

“…Compound 1 is itself prepared by the reaction of Zr(h 5 -C 5 H 5 ) 2 [P 2 (CBu t ) 2 ] with PCl 3 . 3 We have used this molecule as a starting point for several diverse studies and have shown that it provides an atom-efficient route to the triphospholide anion, [P 3 (CBu t ) 2 ] -, 4,5 as well as a route to a species that is a triphosphorus analogue of the cyclopentadienyl cation. 5 Furthermore, the distinctive 31 P NMR signature of 1 in combination with DFT calculations has been utilised to show that nucleophilic substitution of 1 occurs via competing S N 2-type and AE¢ reaction pathways, the latter being a previously unseen substitution pathway in phosphorus chemistry.…”