Synthesis and structural characterization of a tetraaryldiphosphorus cation and a dialkylphosphonium salt

Article abstract of DOI:10.1080/10426509608037969

The compound 5-chorodibenzophosphole reacts with an equivalent amount or an excess of Al₂Cl₆ in methylene chloride solution to afford the respective tetraorganodiphosphorus cations [R₂P(Cl)PR₂][AlCl₄] (R₂ = o,o′-dibenzophenylato), 1. However, reaction of t-Bu₂PCl with an equivalent amount or an excess of Al₂Cl₆ in CH₂Cl₂ gives rise to a phosphonium ion, [t-Bu₂PCl₂][AlCl₄] (2) as the major product, while reaction with 0.5 equivalent Al₂Cl₆ leads to a mixture of cationic organophosphorus species. In addition, the compound 5-chloro-bis-carboranylphosphole (3) was synthesized. Compound 3 fails to react with Al₂Cl₄ or GaCl₃, yet does afford 5-fluoro-bis-carboranylphosphole (4) upon treatment with AgSbF₆. The molecular structures of 1 and 2 have been determined from X-ray structural analysis. The former consists of a planar P(III) heterocyclic moiety joined to an essentially tetrahedral P(IV) heterocycle by a single P - P bond. The charge is balanced by the heptachlorodialuminate ion. Compound 1 crystallized in the triclinic space group Pl with a = 10.5798(8) A, b = 11.3656(9) A, c = 13.8190(11) A, α = 107.985(3)°, β = 100.9135(2)°, γ = 103.636(2)°, V = 1478 A³, Z = 2, R = 0.047. Compound 2 crystallized in the monoclinic space group, P2_l with a = 7.2471(8) A, b = 12.0235(12) A, c =9.9651(11) A, β = 90.473(3)°, V = 868 A³, Z = 2, R = 0.109.

Full text of DOI:10.1080/10426509608037969

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Phosphorus, Sulfur, and Silicon and
the Related Elements
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SYNTHESIS AND STRUCTURAL
CHARACTERIZATION OF A
TETRAARYLDIPHOSPHORUS CATION
AND A DIALKYLPHOSPHONIUM SALT
a
b
Stephen E. Johnson & Carolyn B. Knobler
a
Department of Chemistry , The University of Iowa , Iowa City,
IA, 52242-1294, USA
b
Department of Chemistry and Biochemistry , The University of
California at Los Angeles , Los Angeles, CA, 90024-1569, USA
Published online: 24 Sep 2006.
To cite this article: Stephen E. Johnson & Carolyn B. Knobler (1996) SYNTHESIS AND STRUCTURAL
CHARACTERIZATION OF A TETRAARYLDIPHOSPHORUS CATION AND A DIALKYLPHOSPHONIUM
SALT, Phosphorus, Sulfur, and Silicon and the Related Elements, 115:1, 227-240, DOI:
10.1080/10426509608037969
To link to this article: http://dx.doi.org/10.1080/10426509608037969
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