From the tetra(amino) phosphonium cation, [P(NHPh)4]+, to the tetra(imino) phosphate trianion, [P(NPh)4]3-, two-faced ligands that bind anions and cations

Dalton Transactions : an International Journal of Inorganic Chemistry
Jamie F BickleyStefano Zacchini

Abstract

The tetraanilino phosphonium cation, [P(N(H)Ph)4]+, 1+, is sequentially deprotonated by Bu(n)Li in thf. The deprotonation reaction of the chloride derivative, Cl, was monitored by (31)P NMR, which revealed the successive formation of the neutral [P(N(H)Ph)3(NPh)], 2, the monoanionic [P(N(H)Ph)2(NPh)2]-, 3-, the dianionic [P(N(H)Ph)(NPh)3]2-, 4(2-), and finally the trianionic species [P(NPh)(4)](3-), (3-). Considering the isoelectronic relationship of oxo, =O, and imino groups, =NR, as well as hydroxy, -OH, and amino groups, -N(H)R, the neutral complex corresponds to phosphoric acid, H3PO4, whereas the anions 3-, 4(2-) and 5(3-) are analogues of dihydrogen phosphate, H2PO4-, monohydrogenphosphate, HPO4(2-), and orthophosphate ions, PO4(3-), respectively. Solid state structures were obtained of 1Cl, 2LiCl(thf)(2), 3Li(thf)(3.5), 3Li(2)Cl(thf)(4.25), 3Li(2)Cl(thf)(6) and 5Li(4)Cl(thf)(4). All systems provide two separate N-P-N chelation sites at opposite ligand faces, either consisting of the di(amino) arrangement P(NH)(2), acting as a double H-bond donor, the di(imino) arrangement PN(2), donating two electron pairs, or the mixed amino imino arrangement P(N)(NH), which supplies both electron pair and H-donor site. Interesting in t...Continue Reading

References

Oct 31, 2002·Angewandte Chemie·Justin K. Brask, Tristram Chivers
Dec 20, 2002·Angewandte Chemie·Thomas Steiner
Jul 5, 2003·Chemical Communications : Chem Comm·Philip I RichardsAlexander Steiner

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Citations

Aug 11, 2012·Inorganic Chemistry·Daniel N WoodruffRichard A Layfield
Jan 26, 2008·Chemical Communications : Chem Comm·Mark A BensonAlexander Steiner
Apr 28, 2011·Acta Crystallographica. Section E, Structure Reports Online·Khodayar GholivandSedigheh Farshadian
Jul 7, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Arvind K GuptaRamamoorthy Boomishankar
Dec 15, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Arvind K GuptaRamamoorthy Boomishankar
Sep 11, 2009·Inorganic Chemistry·Bijan NekoueishahrakiDietmar Stalke
Oct 26, 2005·Inorganic Chemistry·Andrea F ArmstrongRené T Boeré

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