Rare earth (RE) complexes of 3-benzoylpropanoate (bp), [RE(bp)3(H2O)n] (RE=La, n=2; RE=Y, Ce, Pr, Nd, Yb, n=1) and 3-phenylpropanoate (pp), [RE(pp)3] (RE=Y, La, Ce, Nd, Yb), have been prepared by metathesis reactions between the corresponding rare earth chloride and the appropriate sodium carboxylate. Analysis by single-crystal X-ray diffraction finds that both RE bp and pp complexes favour formation of carboxylate-bridged 1-D coordination polymers in the solid state. Here, the former favours heteroleptic 9 or 10-coordinate complexes (splitting between Ce and La) with the carbonyl remaining uncoordinated but participating as a hydrogen bond acceptor with water in the coordination sphere. Lack of bp carbonyl coordination leaves this group available for surface interactions during corrosion inhibition and complex solubilization. The latter pp derivatives form eight-coordinate complexes for Y and Yb and are the first examples of homoleptic RE pp complexes to be reported.

A range of rare earth(III) 4-hydroxybenzoato (4hob) complexes has been prepared by salt metathesis reactions in water and structurally characterized by X-ray single crystal and powder diffraction. Complexes in which...

The reaction of bis(pentafluorophenyl)mercury with the ligands bis(diphenylphosphano) methane P,P’-dioxide ({Ph2P(O)}2CH2) (1), bis{2-(N,N,N’N’-tetraethyldiaminophosphano) imidazol-1-yl} methane P,P’-dioxide ({2-PO(NEt2)2C3N2H2}2CH2) (2) and bis (2-diphenylphosphanophenyl) ether P,P’-dioxide ({2-PPh2(O)C6H4}2O) (3) afforded crystalline σ-donor complexes [{Hg(C6F5)2}2{Ph2P(O)}2CH2] (1Hg), [Hg(C6F5)2{2-PO(NEt2)2C3N2H2}2CH2]n (2Hg) and [Hg(C6F5)2{2-PPh2(O)C6H4}2O] (3Hg), respectively. The molecular structures of 1Hg, 2Hg and 3Hg show considerable differences. In complex 1Hg, a single bridging bidentate ligand connects two three-coordinate T-shape mercury atoms with a near linear C-Hg-C atom array. Complex 2Hg is a one-dimensional coordination polymer in which adjacent four-coordinate mercury atoms with a linear C-Hg-C atom array are linked by bridging bidentate O,O’- ligands, whilst in complex 3Hg a T-shape three-coordinate mercury atom is ligated by (3) in a monodentate fashion. The Hg-O bond lengths of complexes 1Hg, 2Hg and 3Hg differ substantially (range 2.5373(14)-2.966(3) Å) owing to structural and bonding differences.

Reaction of [YbCp2(dme)] (Cp = cyclopentadienyl, dme = 1,2 dimethoxyethane) with bis(diphenylphosphano)methane dioxide (H2dppmO2) leads to deprotonation of the ligand H2dppmO2 and oxidation of ytterbium, forming an extremely air-sensitive product, [YbIII(HdppmO2)3] (1), a six-coordinate complex with three chelating (OPCHPO) HdppmO2 ligands. Complex 1 was also obtained by a redox transmetallation/protolysis synthesis from metallic ytterbium, Hg(C6F5)2, and H2dppmO2. In a further preparation, the reaction of [Yb(C6F5)2] with H2dppmO2, not only yielded compound 1, but also gave a remarkable tetranuclear cage, [Yb4(µ-HdppmO2)6(µ-F)6] (2) containing two [Yb(µ-F)]2 rhombic units linked by two fluoride ligands and the tetranuclear unit is encapsulated by six bridging HdppmO2 donors. The fluoride ligands of the cage result from C-F activation of pentafluorobenzene and concomitant formation of p-H2C6F4 and m-H2C6F4, the last being an unexpected product.