Dinuclear Lanthanide(III) Complexes from the Use of Methyl 2-Pyridyl Ketoxime: Synthetic, Structural, and Physical Studies.

The first use of methyl 2-pyridyl ketoxime (mepaoH) in homometallic lanthanide(III) [Ln(III)] chemistry is described. The 1:2 reactions of Ln(NO3)3·nH2O (Ln = Nd, Eu, Gd, Tb, Dy; n = 5, 6) and mepaoH in MeCN have provided access to complexes [Ln2(O2CMe)4(NO3)2(mepaoH)2] (Ln = Nd, 1; Ln = Eu, 2; Ln = Gd, 3; Ln = Tb, 4; Ln = Dy, 5); the acetato ligands derive from the LnIII-mediated hydrolysis of MeCN. The 1:1 and 1:2 reactions between Dy(O2CMe)3·4H2O and mepaoH in MeOH/MeCN led to the all-acetato complex [Dy2(O2CMe)6(mepaoH)2] (6). Treatment of 6 with one equivalent of HNO3 gave 5. The structures of 1, 5, and 6 were solved by single-crystal X-ray crystallography. Elemental analyses and IR spectroscopy provide strong evidence that 2-4 display similar structural characteristics with 1 and 5. The structures of 1-5 consist of dinuclear molecules in which the two LnIII centers are bridged by two bidentate bridging (η1:η1:µ2) and two chelating-bridging (η1:η2:µ2) acetate groups. The LnIII atoms are each chelated by a N,N'-bidentate mepaoH ligand and a near-symmetrical bidentate nitrato group. The molecular structure of 6 is similar to that of 5, the main difference being the presence of two chelating acetato groups in the former instead of the two chelating nitrato groups in the latter. The geometry of the 9-coordinate LnIII centers in 1, 5 and 6 can be best described as a muffin-type (MFF-9). The 3D lattices of the isomorphous 1 and 5 are built through H-bonding, π⋯π stacking and C-H⋯π interactions, while the 3D architecture of 6 is stabilized by H bonds. The IR spectra of the complexes are discussed in terms of the coordination modes of the organic and inorganic ligands involved. The Eu(III) complex 2 displays a red, metal-ion centered emission in the solid state; the TbIII atom in solid 4 emits light in the same region with the ligand. Magnetic susceptibility studies in the 2.0-300 K range reveal weak antiferromagnetic intramolecular GdIII…GdIII exchange interactions in 3; the J value is -0.09(1) cm-1 based on the spin Hamiltonian H = -J(SGd1·SGd2).

Employment of methyl 2-pyridyl ketone oxime in 3d/4f-metal chemistry: dinuclear nickel(II)/lanthanide(III) species and complexes containing the metals in separate ions.

The use of methyl 2-pyridyl ketone oxime (mpkoH) for the synthesis of Ni(II)/Ln(III) (Ln = lanthanide) complexes, using "one-pot" reactions in the absence of an external base, is described. Depending on the reaction and crystallization conditions employed, two families of complexes have been obtained. The first family consists of true heterometallic species and involves complexes [NiLn(mpko)(3)(mpkoH)(3)](ClO(4))(2), where Ln = Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho and Er. The second family contains the pseudo heterometallic complexes [Ni(mpkoH)(3)](2)[Ln(NO(3))(6)](ClO(4)), where Ln = La, Ce, Pr, Nd and Sm. The crystal structures of [NiCe(mpko)(3)(mpkoH)(3)](ClO(4))(2) (1), [NiDy(mpko)(3)(mpkoH)(3)](ClO(4))(2) (8) and [Ni(mpkoH)(3)](2)[La(NO(3))(6)](ClO(4)) (11) have been determined by single-crystal, X-ray crystallography. Complexes 1·1.2MeOH·0.6H(2)O and 8·1.2MeOH·0.6H(2)O crystallise in the monoclinic space group P2(1)/a and are isomorphous; there are two crystallographically independent cations in the unit cell, but their interatomic distances and angles differ little. The Ni(II) and Ln(III) ions are bridged by three oximate groups belonging to the η(1):η(1):η(1):µ mpko(-) ligands. The Ni(II) centre is octahedrally coordinated by the six nitrogen atoms of the mpko(-) ligands in a facial arrangement. The Ln(III) centre is bound to an (O(oximate))(3)N(6) set of donor atoms, the nitrogen atoms belonging to the three N,N'-bidentate chelating mpkoH ligands. The stereochemistry of the Ln(III) atoms has been evaluated by means of continuous shape measures (CShM). The two crystallographically independent Ce(III) atoms in 1 have tricapped trigonal prismatic and capped square antiprismatic coordination geometries, while the polyhedra of the Dy(III) atoms in 8 are both close to a tricapped trigonal prism. The octahedral Ni(II) atoms in 11 are both facially bound to a N(6) set of donor atoms from three N,N'-bidentate chelating mpkoH ligands, while the 12-coordinate La(III) centre in [La(NO(3))(6)](3-) is coordinated by six bidentate chelating nitrato groups. Variable-temperature, solid state dc magnetic susceptibility studies were carried out on complexes 2, 6, 7 and 8. The dc susceptibility data for 6 in the 2.0-300 K range have been fit to a model with one J value, revealing an antiferromagnetic Ni(II)···Gd(III) exchange interaction [J = -1.1 cm(-1) based on H = -J (S(Ni)·S(Gd))]. Antiferromagnetic Ni(II)···Pr(III), Ni(II)···Tb(III) and Ni(II)···Dy(III) exchange interactions have also been suggested for 2, 7 and 8, respectively. The combined work demonstrates the usefulness of mpko(-) in the preparation of interesting Ni(II)/Ln(III) compounds, without requiring the presence of external base and ancillary organic ligands.