Coupling of Silsesquioxane Cages in the Coordination Sphere of Erbium

Lorenz, Volker; Blaurock, Steffen; Hrib, Cristian G.; Edelmann, Frank T.

doi:10.1002/ejic.201000186

Cited by 18 publications

(15 citation statements)

References 38 publications

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“…Surprisingly, when carried out under very similar conditions, the analogous reaction of 40 with anhydrous erbium trichloride took an entirely different course. Compound 40 was first generated by metalation of ( c ‐C 6 H 11 ) 7 Si 7 O 9 (OH) 3 ( 29 ) with 3 equivalents of LiN(SiMe 3 ) 2 , followed by reaction with anhydrous ErCl 3 in THF (Scheme , Cy = cyclohexyl) 48. Insoluble by‐products were separated by extraction with n ‐pentane.…”

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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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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“…Compounds containing various transition and non-transition metals such as Li, K, Be, Al, In, Sc, Sm, Yb, U, Ti, Zr, Ta, Cr, Cu [5], Ca [28], Ti [29], Zr, Yb [30] Mn [31], V [32,33], Nb [34], Er [35], and Ta [36] have been obtained according to Scheme 1. Fe-containing compounds of this type were reviewed in [37].…”

Section: Introduction Of Metal Atoms Into Cage Siloxane Structurementioning

confidence: 99%

“…When one of the Si-OH groups is blocked by OЕR х fragments (Е denotes non-metal), several unusual metal-containing compounds can be obtained based on modified cubane synthones ( Fig. 5; 9, R = c-C 5 H 9, [44]; 10, R = c-C 5 H 9 , [42]; 11, R = c-C 5 H 9 , X =, B(C 6 F 5 ) 2 [45], X = SiMeVin 2 [46]; 12, R = c-C 5 H 9, X = Me 3 , MePh 2 [47]; 13, R = c-C 6 H 11 , [48]; 14, R = c-C 5 H 9 , [49]; 15, R = c-C 6 H 11 , [35] [44] 10 [42] 11 [45] 12 [47] A c c e p t e d M a n u s c r i p t 7 13 [48] 14 [49] 15 [35] This synthetic approach was developed by using a method to obtain an "open" siloxane cage with two Si-OH-groups instead of three. Compound 16 was synthesized in three steps starting with acidic splitting of the closed cubic structure (Scheme 3) [50].…”

Section: Introduction Of Metal Atoms Into Cage Siloxane Structurementioning

confidence: 99%

Modern concepts and methods in the chemistry of polyhedral metallasiloxanes

Levitsky

Bilyachenko

2016

Coordination Chemistry Reviews

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“…Siloxanes and silsesquioxanes can be used as ligands in the formation of a wide variety of interesting metallorganic complexes, for example hybrid complexes of lanthanides and oligosilsesquioxanes192021. Metallasilsesquioxanes contain the functional group Si-O-M, where M can be a main group metal, d -transition metal or f -group element2122232425.…”

mentioning

confidence: 99%

“…Metallasilsesquioxanes contain the functional group Si-O-M, where M can be a main group metal, d -transition metal or f -group element2122232425. Their preparation and interesting properties have been described in several comprehensive reviews in recent years2627282930 and they have been utilized as catalysts industrially227293031.…”

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confidence: 99%

Rare Earth Doped Silica Nanoparticles via Thermolysis of a Single Source Metallasilsesquioxane Precursor

Davies

O’Brien

Gun’ko

2017

Sci Rep

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Rare earth metal doped silica nanoparticles have significant advantages over traditional organic dyes and quantum dots. Silsesquioxanes are promising precursors in the production of silica nanoparticles by thermolysis, due to their structural similarities with silica materials. This manuscript describes the production of a new Eu3+-based metallasilsesquioxane species and its use as a single source precursor in the thermolytic production of luminescent rare earth metal doped silica nanoparticles with characteristic emission in the visible region of the spectrum.

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Coupling of Silsesquioxane Cages in the Coordination Sphere of Erbium

Cited by 18 publications

References 38 publications

Disiloxanediolates and Metallasilsesquioxanes of the Rare Earth Elements

Disiloxanediolates and Metallasilsesquioxanes of the Rare Earth Elements

Modern concepts and methods in the chemistry of polyhedral metallasiloxanes

Rare Earth Doped Silica Nanoparticles via Thermolysis of a Single Source Metallasilsesquioxane Precursor

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