The synthesis of phosphorus heterocycles from tetra-tert-butyltetraphosphacubane

Abstract

Tetra-tert-butyltetraphosphacubane, P(4)C(4)(t)Bu(4), reacts with water in the presence of 'GaI' to yield two products, namely 4,6,7,8-tetra-tert-butyl-1,2,3-triphospha-5-phosphoniatetracyclo[3.2.1.0(2,4).0(3,8)]oct-6-ene tetraiodogallate(III), (C(20)H(37)P(4))[GaI(4)], and triiodo(3,5,7,8-tetra-tert-butyl-1,2,4lambda(5),6-tetraphosphatetracyclo[4.1.1.0(2,5).0(7,8)]octan-4-one)gallium(III), [GaI(3)(C(20)H(38)OP(4))], both of which have been structurally characterized. The X-ray crystal structure determination of the former compound shows it to be an ion-separated salt, while the latter compound is a neutral phosphinite complex of GaI(3).

Phosphines and Related Tervalent Phosphorus Systems

“…625 New phosphorus cage compounds have been isolated from the reactions of tetra-t-butyltetraphosphacubane with water in the presence of gallium(I) iodide. 626 The transformation of the stannylphosphine P(SnMe 3 ) 3 into the P-Sn cage system P 4 (SnMe 2 ) 6 has also been studied. 627 The reactions of the phosphines Me 3 MPMe 2 (M¼Si or Sn) with fluoroarenes, which proceed with displacement of fluorine and introduction of the Me 2 P moiety, have now been applied to p-complexed fluoroarenes 628 and various fluoroquinolines.…”

PC Bonds as Building Blocks for Three‐ and Four‐Membered Heterocyclic Cations: Synthesis, Structures and Mechanistic Studies

“…Although cationic P 2 C 2 rings have been observed within fused polycyclic structures, [23][24][25] www.chemeurj.org phosphetanium [P 2 C 2 R 7 ] + ions. Owing to the disorder present in the structure of [3 b]I, this discussion will focus on the pertinent metrical parameters of [3 a]I, which crystallizes with two unique molecules within the asymmetric unit.…”