Isolation and structural characterization of the first homoleptic lanthanide–zirconium oxoisopropoxide, La2Zr3O(OPri)16. Combination of an [M4O] tetrahedron with an [MO6] octahedron – A new structure type for pentanuclear alkoxide complexes

Turova, Nataliya; Kessler, Vadim G.; Turevskaya, E. P.; Yanovsky, A.I.

doi:10.1016/j.inoche.2006.12.002

Cited by 4 publications

(1 citation statement)

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“…Until now, the structures of only 31 such compounds have been deposited in the Cambridge Structural Database . Most of them (29) are isopropoxide or ethoxide derivatives of formula [Ln 4 Ti(O)(O i Pr) 14 ] (Ln = Sm and Tb), , [Ln 2 Zr 4 (O i Pr) 18 (Cl) 4 ] (Ln = Nd, Ho, and Ce), [CpLnZr 2 (O i Pr) 9 ] (Ln = Yb and Sm), [LnZr 2 (O i Pr) 9 (X) 2 ] (Ln = Tm, Er, and Yb; X = Cl and I), [La 2 Zr 3 (O)(O i Pr) 16 ], [Ln 2 Ti 4 (O) 2 (OEt) 16 (HOEt) 2 (Cl) 2 ] (Ln = Ce, Eu, and Nd), − [LnTi 8 (O) 7 (OEt) 21 (HOEt) x ] (Ln = Ce and Er and x = 0 and 1), , [PrTi 29 (O) 38 (OEt) 40 (Br)], [LnTi 28 (O) 36 (OEt) 40 (OH) 2 (Cl)] (Ln = Ce and La), and [LnTi 11 (O) 16 (NO 3 ) 2 (O i Pr) 17 ] (Ln = Sm, Eu, and Gd) . Of these heterometallic clusters, 15 are zirconium, and 16 are titanium derivatives.…”

Section: Introductionmentioning

confidence: 99%

Heterometallic Group 4–Lanthanide Oxo-alkoxide Precursors for Synthesis of Binary Oxide Nanomaterials

et al. 2020

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In this study, an efficient procedure for the synthesis of uncommon group 4–lanthanide oxo-alkoxide derivatives was developed. Heterometallic clusters with the structures [La2Ti4(μ4-O)2(μ3-OEt)2(μ-OEt)8(OEt)6(Cl)2(HOEt)2] (1), [La2Zr2(μ3-O)(μ-OEt)5(μ-Cl)(OEt)2(HOEt)4(Cl)4] n (2), [La2Hf2(μ3-O)(μ-OEt)5(μ-Cl)(OEt)2(HOEt)4(Cl)4] n (3), [Nd2Ti4(μ4-O)2(μ3-OEt)2(μ-OEt)8(OEt)6(HOEt)2(Cl)2] (4), [Nd4Zr4(μ3-O)2(μ-OEt)10(μ-Cl)4(OEt)8(HOEt)10(Cl)2] (5), and [Nd4Hf4(μ3-O)2(μ-OEt)10(μ-Cl)4(OEt)8(HOEt)10(Cl)2] (6) were synthesized via the reaction of a metallocene dichloride, Cp2M′Cl2 (where M′ = Ti, Zr, and Hf), and metallic lanthanum or neodymium in the presence of excess ethanol. This procedure gave crystalline precursors with molecular stoichiometries suitable for obtaining group 4–lanthanide oxide materials. Compounds 1–6 were examined by analytical and spectroscopic techniques and single-crystal X-ray diffraction. The magnetic properties of 5 and 6 were investigated by using direct and alternating current (dc and ac) susceptibility measurements. The results indicated weak antiferromagnetic interactions between NdIII ions and a field-supported slow magnetic relaxation. Lanthanum–titanium compound 1 decomposed at 950 °C to give the perovskite compound La0.66TiO3 and small amounts of rutile TiO2. Under the same conditions, 4 decomposed to give a mixture of Nd4Ti9O24 and Nd0.66TiO3. When 4 was calcined at 1300 °C, decomposition of Nd4Ti9O24 to Nd0.66TiO3 and TiO2 was observed. Calcination of 2, 3, 5, and 6 at 950–1500 °C led to the selective formation of heterometallic La2Zr2O7, La2Hf2O7, Nd2Zr2O7, and Nd2Hf2O7 phases, respectively.

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Section: Introductionmentioning

confidence: 99%

Heterometallic Group 4–Lanthanide Oxo-alkoxide Precursors for Synthesis of Binary Oxide Nanomaterials

et al. 2020

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A Pentanuclear Cu/Co/Ni Complex with 2‐(Dimethylamino)ethanol – Observation of a Rare Molecular Structure Type and Its Place in General Structural Types: An Analysis of the Cambridge Structural Database

2009

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Heterotrimetallic complex [CuII2CoIINiII2(Me2Ea)5Cl5(H2O)]·CH3CN·H2O has been prepared in a one‐pot reaction of zero‐valent copper with cobalt and nickel chlorides in an acetonitrile solution of 2‐(dimethylamino)ethanol (HMe2Ea) in the open air. The metal stoichiometry obtained by atomic absorption analysis was further confirmed by single‐crystal X‐ray diffraction investigations. The pentanuclear molecule is formed by a previously unknown combination of incomplete cube M3(μ3‐X)(μ‐X)3 and triangle bipyramidal M3(μ3‐X)2(μ‐X)2 fragments, resulting in a zigzag arrangement of metal centers within one molecule. This type of arrangement is very uncommon for pentanuclear complexes and in particular for complexes with an odd number of metal centers. A search of the Cambridge Structural Database showed that the number of coordination compounds possessing an even number of metals is significantly greater than those containing an odd number. Possible reasons for such a distribution, as well as the synthetic and structural features of the presented compound, are discussed.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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Titanium, zirconium and hafnium

Cotton¹

2008

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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This chapter reviews the literature reported during 2007 on titanium, zirconium and hafnium. Because of the limitations of space, this review is very selective, and much fine work has not been cited, especially in the area of organometallic chemistry. HighlightsHighlights include significant developments in dinitrogen complexes, [79][80][81][82] whilst burgeoning interest in TiO 2 is sustained. 11,13,15,18

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Isolation and structural characterization of the first homoleptic lanthanide–zirconium oxoisopropoxide, La2Zr3O(OPri)16. Combination of an [M4O] tetrahedron with an [MO6] octahedron – A new structure type for pentanuclear alkoxide complexes

Cited by 4 publications

References 20 publications

Heterometallic Group 4–Lanthanide Oxo-alkoxide Precursors for Synthesis of Binary Oxide Nanomaterials

Heterometallic Group 4–Lanthanide Oxo-alkoxide Precursors for Synthesis of Binary Oxide Nanomaterials

A Pentanuclear Cu/Co/Ni Complex with 2‐(Dimethylamino)ethanol – Observation of a Rare Molecular Structure Type and Its Place in General Structural Types: An Analysis of the Cambridge Structural Database

Titanium, zirconium and hafnium

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