Complexes of phosphine-phenolate ligands with the [Re=O](3+) and [Re(HNNC5H4N)(NNC5H4N)](2+) cores

Complexes incorporating the [Re=O](3+) core have been synthesised with liga nds containing the new methyl substituted phosphine-phenolate PO and PO2 do nor sets, (2-hydroxy-5-methylphenyl) diphenylphosphine (H(MePO)) and bis(2- hydroxy-5-methylphenyl) phenylphosphine (H-2(Me2PO2)). The analogous tert-b utyl ligands, (5-tert-butyl-2-hydroxyphenyl)diphenylphosphine (H(t-BuPO)) a nd bis(5-tert-butyl-2-hydroxyphenyl) phenylphosphine (H-2 (t-Bu2PO2)), were also prepared. Reaction of either mer-[ReOCl3 (PPh3)(2)] or [NH4][ReO4] in CH3OH with H(MePO) led to formation of [ReOCl(MePO)(2)] (1) in good yield. Reaction of [NH4][ReO4] with H-2 (Me2PO2) in CH3OH afforded [ReO(Me2PO2)(H (Me2PO2))] (2), also in good yield. X-Ray crystallographic analyses of 1 an d 2 demonstrated that both complexes are neutral and octahedral, and contai n the oxo moiety. Two complexes have been structurally characterised from t he reaction of (o-hydroxyphenyl) diphenylphosphine (HPO) with [Re(Hhypy)(hy pyH)Cl-3]: [Re(Hhypy)(hypy)(PO)(HPO)]Cl (3) and [ReCl(Hypy)(hypy)(PO)] (4) (hypy = NNC5H4N, Hhypy = HNNC5H4N, hypyH = NNC5H4NH). X-Ray crystallography demonstrated that both are Re(III) complexes; 3 is monocationic with an N3 OP2 coordination sphere while 4 is neutral with a ClN3OP coordination spher e. [Re(Hhypy)(hypy)(HPO2)(H2PO2)] Cl (5) and [Re(Hhypy)(hypy)(H(Me2PO2))(H- 2 (Me2PO2))] Cl (6) were synthesised by reaction of [Re(Hhypy)(hypyH)Cl-3] in CH3OH with bis(o-hydroxyphenyl) phenylphosphine (H2PO2) and H-2(Me2PO2) respectively. Compounds 5 and 6 were shown by H-1 and P-31 NMR spectroscopi es to have the same N3OP2 coordination sphere as [Re(Hhypy)(hypy)(PO)(HPO)] Cl, with the addition of several uncoordinated, protonated phenolic donors .