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Synthesis, reactivity and structural characterisation of bicyclic tetraphosphapentazanes

Thirupathi, Natesan and Krishnamurthy, Setharampattu S and Nethaji, Munirathinam (1998) Synthesis, reactivity and structural characterisation of bicyclic tetraphosphapentazanes. In: Dalton Transactions (09). pp. 1469-1475.

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The diphenoxy bicyclic tetraphosphapentazane derivatives (EtN)(5)P-4(OPh)(2) 2 and its monoxide (EtN)(5)P-4(O)(OPh)(2) 3 have been prepared. Both 2 and 3 exist as a mixture of two isomers. One isomer of (EtN)(5)P-4(O)(OPh)(2) 3a has been isolated and its reaction with tetrachloro-1,2-benzoquinone yielded (EtN)(5)P-4(O)(OPh)(2)(O2C6Cl4) 5 in which the junction phosphorus atom becomes five-co-ordinated. Treatment of 2 or 3a with [Mo(CO)(4)(nbd)] (nbd = norbornadiene, bicyclo[2.2.1]hepta-2,5-diene), on the other hand, yielded the chelate complex [Mo(CO)(4){(EtN)(5)P-4(O)(n)(OPh)(2)}] (n = 0 or 1; 6 or 7) in which the peripheral phosphorus atoms are bonded to the metal. The structures of 3a and 5-7 have been confirmed by single-crystal X-ray diffraction studies. The two P3N3 rings in 3a and 5 adopt twist/twist and irregular/twist conformations respectively; the phenoxy substituents occupy the 'pseudo axial' positions. However, an ideal chair conformation is observed for the P3N3 rings in 6 and 7 with the phenoxy substituents taking up the 'pseudo equatorial' positions. The NMR spectroscopic data for the compounds are discussed.

Item Type: Journal Article
Publication: Dalton Transactions
Publisher: Royal Society of Chemistry
Additional Information: Copyright of this article belongs to Royal Society of Chemistry.
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 07 Jan 2010 07:12
Last Modified: 19 Sep 2010 05:28
URI: http://eprints.iisc.ac.in/id/eprint/19394

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