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DOI: 10.1039/A801443D (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 1469-1476

Synthesis, reactivity and structural characterisation of bicyclic tetraphosphapentazanes

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Natesan Thirupathi, Setharampattu S. Krishnamurthy and Munirathinam Nethaji

Abstract

The diphenoxy bicyclic tetraphosphapentazane derivatives (EtN)5P4(OPh)2 2 and its monoxide (EtN)5P4(O)(OPh)2 3 have been prepared. Both 2 and 3 exist as a mixture of two isomers. One isomer of (EtN)5P4(O)(OPh)2 3a has been isolated and its reaction with tetrachloro-1,2-benzoquinone yielded (EtN)5P4(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)5P4(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.

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