Synthesis of the 2,4,5-tri-tert-butyl-1, 3-diphospholyl anion, P2C3But3-via phosphinidene elimination from 2, 4, 6 tri-tert-butyl-1, 3, triphosphabenzene, P3C3But3, on treatment with the amide Li[NPh(SiMe3)]

Clendenning, Scott B, Hitchcock, Peter B, Lappert, Michael F, Merle, Philippe G, Nixon, John F and Nyulazi, Laszlo (2007) Synthesis of the 2,4,5-tri-tert-butyl-1, 3-diphospholyl anion, P2C3But3-via phosphinidene elimination from 2, 4, 6 tri-tert-butyl-1, 3, triphosphabenzene, P3C3But3, on treatment with the amide Li[NPh(SiMe3)]. Chemistry - A European Journal, 13 (25). pp. 7121-7128. ISSN 0947-6539

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Abstract

Treatment of the lithium amide Li[NPh(SiMe3)] with 2,4,6-tri-tert-butyl-1,3,5-triphosphabenzene, P3C3tBu3, in a 1:2 ratio afforded equimolar amounts of the lithium salt of the five-membered 2,4,5-tri-tert-butyl-1,3-diphospholide anion, LiP2C3tBu3 (isolated as its N,N,N′,N′-tetramethylethylenediamine (TMEDA) adduct), and the tricyclic compound 6-[phenyl(trimethylsilyl)amino]-3,5,7-tri-tert-butyl-1,2,4,6-tetraphosphatricyclo[3.2.0.02,7]hept-3-ene. Both compounds have been structurally characterised by single-crystal X-ray diffraction studies. The mechanism of this remarkable reaction has been elucidated by theoretical methods at the B3LYP/6-311+G** level of theory. The reaction involves a hitherto unobserved aminophosphinidene, which was formed by abstraction of a phosphorus atom from triphosphabenzene. The intermediate aminophosphinidene, which is further stabilised by the solvent THF, shows, in agreement with previous theoretical predictions, enhanced stability and reacts then with a second molecule of triphosphabenzene.

Item Type: Article
Additional Information: JN supervised the synthesis work in collaboration with ML and is joint corresponding author
Schools and Departments: School of Life Sciences > Chemistry
Depositing User: John Nixon
Date Deposited: 06 Feb 2012 21:18
Last Modified: 12 Jun 2012 15:22
URI: http://sro.sussex.ac.uk/id/eprint/30703
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