Synthesis and molecular structure of a tetrameric neodymium-silsesquioxane cage complex: {[(i-C4H9)7(Si7O12) Nd]4NaCl}

Wu, Guangming; Chen, Yaofeng; Xü, Dong; Liu, Jia-Chu; Sun, Wen‐Hua; Shen, Zhiquan

doi:10.1016/j.jorganchem.2009.01.042

Cited by 22 publications

(8 citation statements)

References 26 publications

(26 reference statements)

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“…Note that the Tb 3+ ‐ containing CLMSs have never been reported up to now. Moreover, all these lanthanide‐containing CLMSs have been regarded especially as model compounds for catalysis [15a–f, h] or components of catalytic systems [15g] . Yet, their optical and magnetic properties have never been investigated.…”

Section: Methodsmentioning

confidence: 99%

New Luminescent Tetranuclear Lanthanide‐Based Silsesquioxane Cage‐Like Architectures

Kulakova

Bilyachenko

Levitsky

et al. 2020

Chemistry A European J

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The synthesis, structure, magnetic, and luminescence properties investigations of four new cage‐like lanthanide‐based silsesquioxanes (Cat)2[(PhSiO1.5)8(LnO1.5)4(O)(NO2.5)6(EtOH)2(MeCN)2] (where Cat+=Et4N+, PPh4P+ and Ln3+=Eu3+, Tb3+ and (Ph4P)4[(PhSiO1.5)8(TbO1.5)4(O)2(NO2.5)8]⋅10MeCN are reported. They present an unusual prism‐like topology of cage architectures and lanthanide‐characteristic emission, which makes them the first luminescent cage‐like lanthanide silsesquioxanes. One of the Tb3+‐based cages presents a magnetic spin‐flip transition.

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Section: Methodsmentioning

confidence: 99%

New Luminescent Tetranuclear Lanthanide‐Based Silsesquioxane Cage‐Like Architectures

Kulakova

Bilyachenko

Levitsky

et al. 2020

Chemistry A European J

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“…Specific representatives of cage metallacomplexes, namely cagelike metallasilsesquioxanes (CLMSs), are being intensely studied as (pre)catalysts for numerous chemical processes of high relevance . Cage metallasilsesquioxanes were found to be active in alkene polymerization, epoxidation or epoxide ring opening, metathesis, hydroformylation, Ullmann–Goldberg condensation and amidation . Recently, significant attention was drawn to the potential of CLMS application in the homogeneous oxidation of C–H compounds with activity confirmed for Fe‐,, Cr‐, Ni‐, and Co‐based compounds.…”

Section: Introductionmentioning

confidence: 99%

Heptanuclear Cage Cu^II‐Silsesquioxanes: Synthesis, Structure and Catalytic Activity

et al. 2018

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Two prismatic phenyl-(PhSiO 1.5 ) 14 (CuO) 7 (1, 29 % yield) and methyl-(MeSiO 1.5 ) 14 (CuO) 7 (2, 19 % yield) heptacoppersilsesquioxanes were obtained by the interaction of Cu,Na-based cage silsesquioxanes [(RSiO 1.5 ) 12 (CuO) 4 (NaO 0.5 ) 4 ] (R = Ph, Me) with 4,4′-bipyridine and pyrazine, respectively, acting as "silent witness" ligands. Unusual molecular topologies of both compounds 1 and 2, which are the first representatives of [a] Nesmeyanov Institute of Organoelement Compounds,

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“…The four neodymium–silsesquioxane cages of 46 are linked by multiple Nd–O–Nd and Nd–Cl–Nd units. A preliminary study showed that the complex is active for highly cis ‐1,4 polymerization of isoprene (92 % selectivity) in the presence of AlEt 3 and Me 3 SiCl 47.…”

Section: Metallasilsesquioxanes Of the Lanthanidesmentioning

confidence: 99%

Disiloxanediolates and Metallasilsesquioxanes of the Rare Earth Elements

Lorenz

Edelmann

Gießmann

et al. 2010

Zeitschrift anorg allge chemie

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This research report summarizes recent results in the chemistry of lanthanide disiloxanediolates and metallasilsesquioxanes. Both classes of compound can be regarded as realistic model compounds for silica-supported lanthanide catalysts. Heterobimetallic siloxanediolates of the lanthanidesThe chemistry of metallasiloxanes derived from silanediols, disiloxanediols and related Si-OH species continues to be an area of vigorous research activities [1][2][3][4][5][6][7] Lanthanide(III) disiloxanediolates a) Lanthanide(III) mono(disiloxanediolates)By now, the chemistry of lanthanide bis(disiloxanediolates) is well established, and some lanthanide tris(disiloxanediolates) have also been prepared and structurally characterized (vide infra) [9]. Only the synthesis of mono-substituted rare earth metal complexes derived from difunctional siloxanediolate ligands had not been achieved until recently. Thus far only one compound of this type has been synthesized and structurally 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 Scheme 1An X-ray study confirmed the presence of the first mono(trisiloxanediolate) complex of a lanthanide element. The molecule contains a puckered eight-membered for hafnium and uranium [6,7,9]. In these cases, however, the trisiloxanediolate ligand is formed by ring-enlargement reactions starting from disiloxanediolate precursors. A prominent structural feature of compound 5 is the presence of a so-called "ate" complex resulting from retention of lithium chloride. "Ate" complexes are a common phenomenon in organolanthanide chemistry. Their formation involves retention of alkali halides formed during the course of a reaction, thereby reflecting the strong tendency of the large lanthanide ions to achieve high coordination numbers [11]. In compound 5 the situation is such that a complex of the type "[Ph 2 Si(OSiPh 2 O) 2 ]YbCl" is sterically highly unsaturated (coordination number 3 at Yb). In this case stabilitzation is achieved not only by coordination of one THF ligand but also through "ate" complex formation with retention of two equivalents of LiCl. One lithium chloride is connected to the central ytterbium via two bridging chloride ligands. The second LiCl is coordinated in a rather peculiar way by additional coordination of a siloxide oxygen atom to Li. In both cases, the coordination sphere around lithium is supplemented by two THF ligands (Fig. 1) [10]. Page 4 of 53Wiley-VCH ZAAC 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 Accordingly these complexes have been termed "metallacrown" derivatives of scandium and yttrium [9]. In contrast, large Ln 3+ ions such as Pr 3+ , Nd 3+ or Sm 3+ do no fit into the center of the twelve-membered ...

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Synthesis and molecular structure of a tetrameric neodymium-silsesquioxane cage complex: {[(i-C4H9)7(Si7O12) Nd]4NaCl}

Cited by 22 publications

References 26 publications

New Luminescent Tetranuclear Lanthanide‐Based Silsesquioxane Cage‐Like Architectures

New Luminescent Tetranuclear Lanthanide‐Based Silsesquioxane Cage‐Like Architectures

Heptanuclear Cage Cu^II‐Silsesquioxanes: Synthesis, Structure and Catalytic Activity

Disiloxanediolates and Metallasilsesquioxanes of the Rare Earth Elements

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Synthesis and molecular structure of a tetrameric neodymium-silsesquioxane cage complex: {[(i-C4H9)7(Si7O12) Nd]4NaCl}

Cited by 22 publications

References 26 publications

New Luminescent Tetranuclear Lanthanide‐Based Silsesquioxane Cage‐Like Architectures

New Luminescent Tetranuclear Lanthanide‐Based Silsesquioxane Cage‐Like Architectures

Heptanuclear Cage CuII‐Silsesquioxanes: Synthesis, Structure and Catalytic Activity

Disiloxanediolates and Metallasilsesquioxanes of the Rare Earth Elements

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Heptanuclear Cage Cu^II‐Silsesquioxanes: Synthesis, Structure and Catalytic Activity