Reactivity of lanthanocene hydroxides toward carbodiimide and CO2: Synthesis and characterization of lanthanide ureido and carbonate complexes

Liu, Ruiting; Li, Zhen; Yi, Weiyin; Chen, Zhenxia; Zhou, Xigeng

doi:10.1016/j.jorganchem.2011.04.016

Cited by 3 publications

(3 citation statements)

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“…All the (NN fc )MBn(THF) and (NN fc )MI(THF) z complexes were characterized by X-ray crystallography. Structurally characterized organometallic complexes of holmium, − erbium, − and gadolinium ,− are rare. (NN fc )NdBn(THF) (Figure SX5), (NN fc )GdBn(THF) (Figure SX6), (NN fc )HoBn(THF) (Figure ), and (TBS)ErBn(THF) (Figure SX8) are isostructural with (NN fc )YBn(THF) .…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Characterization of Paramagnetic Lanthanide Benzyl Complexes

et al. 2013

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The organometallic chemistry of paramagnetic lanthanides (Ln, from Ce to Yb) is far less developed compared to that of their diamagnetic counterparts (Sc, Y, La, and Lu). Lack of available starting materials and characterization methods are the major obstacles. Herein we report the synthesis and characterization of trisbenzyl complexes of neodymium, gadolinium, holmium, and erbium. In addition, we introduce a direct procedure for the synthesis of lanthanide benzyl and iodide complexes supported by a ferrocene diamide ligand starting from the corresponding oxides. All newly synthesized compounds were characterized by X-ray crystallography, 1 H NMR spectroscopy (except for gadolinium compounds, which were NMR silent), and elemental analysis.

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Section: Resultsmentioning

confidence: 99%

Synthesis and Characterization of Paramagnetic Lanthanide Benzyl Complexes

et al. 2013

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“…Monoanionic ureide ligands of the general form shown in Figure have a range of possible coordination behaviors, from κ 2 -chelating ( I , ,, II , and III ,, ) or bridging μ 2 -κ- N , O ( IV ) − and μ–η 1 :η 2 ( VII ) to face capping-chelating μ 3 -η 2 ( VIII ) modes, offering a greater structural diversity when coordinated to main group, transition metal, and f-block elements, than the related carboxylate, amidinate, or guanidinate ligands, all of which have been more extensively studied than ureide ligands. To the best of our knowledge, potential bridging μ 2 -κ- N , N ′ modes V and VI have yet to be observed.…”

Section: Introductionmentioning

confidence: 99%

“…17 To date, only three precursors capable of depositing phase pure SnO using atomic layer deposition (ALD), i.e., [Sn{OCMe 2 CH 2 NMe 2 } 2 ] 18 (Figure 1E), [Sn{OC( t Bu) NOEt} 2 ] 19,20 (Figure 1F), and [Sn{N( t Bu)CMe 2 CH 2 N-( t Bu)} 2 ] 21 (Figure 1G), have been realized. Monoanionic ureide ligands of the general form shown in Figure 2 have a range of possible coordination behaviors, from κ 2 -chelating (I, 17,22,23 II, 24 and III 17,24,25 ) or bridging μ 2 -κ-N,O (IV) 26−28 and μ−η 1 :η 2 (VII) 29 to face capping-chelating μ 3 -η 2 (VIII) modes, 30 offering a greater structural diversity when coordinated to main group, transition metal, and f-block elements, than the related carboxylate, amidinate, or guanidinate ligands, all of which have been more extensively studied than ureide ligands. To the best of our knowledge, potential bridging μ 2 -κ-N,N′ modes V and VI have yet to be observed.…”

Section: ■ Introductionmentioning

confidence: 99%

Tin(II) Ureide Complexes: Synthesis, Structural Chemistry, and Evaluation as SnO Precursors

et al. 2021

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In an attempt to tailor precursors for application in the deposition of phase pure SnO, we have evaluated a series of tin (1–6) ureide complexes. The complexes were successfully synthesized by employing N,N′-trialkyl-functionalized ureide ligands, in which features such as stability, volatility, and decomposition could be modified with variation of the substituents on the ureide ligand in an attempt to find the complex with the ideal electronic, steric, or coordinative properties, which determine the fate of the final products. The tin(II) ureide complexes 1-6 were synthesized by direct reaction [Sn{NMe2}2] with aryl and alkyl isocyanates in a 1:2 molar ratio. All the complexes were characterized by NMR spectroscopy as well as elemental analysis and, where applicable, thermogravimetric (TG) analysis. The single-crystal X-ray diffraction studies of 2, 3, 4, and 6 revealed that the complexes crystallize in the monoclinic space group P2(1)/n (2 and 4) or in the triclinic space group P-1 (3 and 6) as monomers. Reaction with phenyl isocyanate results in the formation of the bimetallic species 5, which crystallizes in the triclinic space group P-1, a consequence of incomplete insertion into the Sn-NMe2 bonds, versus mesityl isocyanate, which produces a monomeric double insertion product, 6, under the same conditions, indicating a difference in reactivity between phenyl isocyanate and mesityl isocyanate with respect to insertion into Sn-NMe2 bonds. The metal centers in these complexes are all four-coordinate, displaying either distorted trigonal bipyramidal or trigonal bipyramidal geometries. The steric influence of the imido-ligand substituent has a clear effect on the coordination mode of the ureide ligands, with complexes 2 and 6, which contain the cyclohexyl and mesityl ligands, displaying κ2-O,N coordination modes, whereas κ2-N,N′ coordination modes are observed for the sterically bulkier tert-butyl and adamantyl derivatives, 3 and 4. The thermogravimetric analysis of the complexes 3 and 4 exhibited excellent physicochemical properties with clean single-step curves and low residual masses in their TG analyses suggesting their potential utility of these systems as MOCVD and ALD precursors.

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Lanthanides and actinides: Annual survey of their organometallic chemistry covering the year 2011

Edelmann

2013

Coordination Chemistry Reviews

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Reactivity of lanthanocene hydroxides toward carbodiimide and CO2: Synthesis and characterization of lanthanide ureido and carbonate complexes

Cited by 3 publications

References 55 publications

Synthesis and Characterization of Paramagnetic Lanthanide Benzyl Complexes

Synthesis and Characterization of Paramagnetic Lanthanide Benzyl Complexes

Tin(II) Ureide Complexes: Synthesis, Structural Chemistry, and Evaluation as SnO Precursors

Lanthanides and actinides: Annual survey of their organometallic chemistry covering the year 2011

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