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DOI: 10.1039/A702500I (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 3397-3402

Co-ordination chemistry of the mixed phosphorus(III)–phosphorus(V) phosphazene ligand Ph2PNP(Ph)2P(Ph)2NPPh2: crystal structures of cis-[Pt(CH3)X{Ph2PNP(Ph)2 P(Ph)2NPPh2-P,P′ }] (X = CH3 or I)

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Alexandra M. Z. Slawin, Martin B. Smith and J. Derek Woollins

Abstract

The ligand Ph2PNP(Ph)2P(Ph)2NPPh2 I was smoothly oxidised at both terminal PPh2 moieties with either elemental sulfur or grey selenium to give Ph2P(E)NP(Ph)2P(Ph)2NP(E)Ph2 (E = S II or Se III) in good yields. Oxidation of I with either aqueous H2O2 (30% w/w) or ButOOH (in decane) gave the known dioxide compound [Ph2P(O)]2NH presumably via a sequence of oxidation, protonation and P–P bond-cleavage reactions. Complexation of I to several palladium(II), platinum(II) and gold(I) starting materials, at ambient temperature, afforded new metal complexes in which I adopts either P,P′-chelating or P,P′-bridging co-ordination modes. Reaction of I (1 equivalent) with the zerovalent compounds [M(PPh3)4] (M = Pt or Pd) in toluene proceeded cleanly, with P–P bond cleavage, and formation of the known four-membered metallacycles [M(Ph2PNPPh2-P,P′)2 ]. All compounds were characterised by a combination of IR and NMR (1H, 31P-{1H}, 195Pt-{1H}) spectroscopy and elemental analyses. Furthermore, the molecular structures of cis-[Pt(CH3)X{Ph2PNP(Ph)2 P(Ph)2NPPh2-P,P′ }] (X = CH3 or I) have been determined by single-crystal X-ray diffraction and represent the first examples of MP4N2 metallacycles incorporating a late transition metal. The PtP4N2 rings in both compounds adopt ‘tub-like’ geometries.

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