Phosphaniminato-Komplexe von Seltenerdelementen. Die Kristallstrukturen von [Yb2Cp3(NPPh3)3], [YCp(NPPh3)(μ-OSiMe2NPPh3)]2 und [M(NPPh3)2(μ-OSiMe2NPPh3)]2 mit M = Y und Sm

Anfang, S.; Gröb, Thorsten; Harms, Klaus; Seybert, Gert; Massa, Werner; Greiner, Andreas; Dehnicke, Kurt

doi:10.1002/(sici)1521-3749(199911)625:11<1853::aid-zaac1853>3.0.co;2-4

Cited by 24 publications

(14 citation statements)

References 6 publications

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“…Base-free bis(trimethylsilyl)amido complexes containing a linked amido-cyclopentadienyl ligand [Ln-(η 5 65 The reaction of ytterbocene chloride with lithium triphenylphosphoraneimidate in toluene gave the crystallographically characterized homobimetallic complex [Yb(η 5 -C 5 H 5 ) 2 (µ-NPPh 3 ) 2 Yb(η 5 -C 5 H 5 )(NPPh 3 )] in which an ytterbocene phosphoraneimidate fragment is connected to a mono(cyclopentadienyl) bis-(phosphoraneiminato) ytterbium fragment through two bridging phosphoraneiminato nitrogen atoms. 66 Azobenzene Complexes. Oxidation of [Sm(η 5 -C 9 H 7 ) 2 (THF) x ] with azobenzene gave a compound of composition [Sm(η 5 -C 9 H 7 )(N 2 Ph 2 )(THF)] x , which is expected to be analogous to the previously structurally characterized C 5 Me 5 analogue [Sm(η 5 -C 5 Me 5 )-(THF)(µ-η 2 :η 2 -N 2 Ph 2 )] 2 .…”

Section: Bis(amido) Complexesmentioning

confidence: 99%

Mono(cyclopentadienyl) Complexes of the Rare-Earth Metals

2002

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Section: Bis(amido) Complexesmentioning

confidence: 99%

Mono(cyclopentadienyl) Complexes of the Rare-Earth Metals

2002

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“…They crystallize isotypically with each other and were obtained in boiling toluene in almost quantitative yield according to Equation (9) 59. 60…”

Section: Complexes Of Rare‐earth Ions Ln3+ With Low Coordination Nmentioning

confidence: 99%

“…They are able to break down linear arranged silicones (‐OSiMe 2 ) n or hexamethyltrisiloxane (OSiMe 2 ) 3 by insertion of monomeric OSiMe 2 groups into the LnN bond [Eq. (12)] 60…”

Section: Complexes Of Rare‐earth Ions Ln3+ With Low Coordination Nmentioning

confidence: 99%

Unusual Complex Chemistry of Rare‐Earth Elements: Large Ionic Radii—Small Coordination Numbers

2003

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Because of their large ionic radii and relatively low oxidation states rare-earth elements generally form complexes which have high coordination numbers and weak metal-ligand bonds. They are often not suitable for homogeneous catalysis on account of their instability of configuration in solution. Complexes of the corresponding metal atoms with low coordination numbers may be an improvement. This type of complex can be obtained in the classical way by the introduction of bulky ligands, and recently, they were also prepared in reactions with ligand groups which offer remarkable metal-ligand bond features. This concept is demonstrated for complexes with bulky bis(trimethylsilyl)amido ligands [N(SiMe(3))(2)](-) and "slim" phosphoraneiminato ligands (NPR(3)(-)). Their suitability as catalysts for the ring-opening polymerization of lactones is reported as well.

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“…Heterocubane structures are fairly rare in organolanthanide chemistry. Prominent examples include the phosphoraneiminato complexes (COT) Ln Li 3 Cl 2 (NPPh 3 ) 2 (THF) 3 ( Ln Li 3 Cl 2 N 2 heterocubanes) 14 and the organolanthanide imido complexes [(C 5 H 4 SiMe 3 ) Ln (μ 3 ‐NCH 2 R)] 4 ( Ln = Y, Lu; R = Me, Ph) ( Ln 4 N 4 heterocubanes) 15.…”

Section: Heterobimetallic Siloxanediolates 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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Phosphaniminato-Komplexe von Seltenerdelementen. Die Kristallstrukturen von [Yb2Cp3(NPPh3)3], [YCp(NPPh3)(μ-OSiMe2NPPh3)]2 und [M(NPPh3)2(μ-OSiMe2NPPh3)]2 mit M = Y und Sm

Cited by 24 publications

References 6 publications

Mono(cyclopentadienyl) Complexes of the Rare-Earth Metals

Mono(cyclopentadienyl) Complexes of the Rare-Earth Metals

Unusual Complex Chemistry of Rare‐Earth Elements: Large Ionic Radii—Small Coordination Numbers

Disiloxanediolates and Metallasilsesquioxanes of the Rare Earth Elements

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