Neue Übergangsmetallcluster‐Komplexe mit Liganden der fünften und sechsten Hauptgruppe

Fenske, Dieter; Ohmer, Johannes; Hachgenei, Johannes; Merzweiler, Kurt

doi:10.1002/ange.19881001006

Cited by 95 publications

(12 citation statements)

References 185 publications

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“…["] If however a T H F solution of S(SiMe,), is allowed to diffuse into a T H F solution of [CpTaCI,] the salt 45 can be isolated in high yield. 44 ( Fig. 16b) The cation of 45 ( Fig.…”

Section: Clusters Of Electron-deficient Transition Metals With Cp Ligmentioning

confidence: 98%

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New Transition Metal Clusters with Ligands from Main Groups Five and Six

Fenske¹,

Ohmer²,

Hachgenei³

et al. 1988

Angew. Chem. Int. Ed. Engl.

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194

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Dedicated to Professor Hans Bock on the occasion of his 60th birthdayIn both physics and chemistry, increased attention is being paid to metal clusters. One reason for this attitude is furnished by the surprising results that have been obtained from studies of the preparation, structural characterization and physical and chemical properties of the clusters. Whereas investigations of cluster reactivity are at present generally limited to three-or four-membered clusters, successful syntheses of clusters with many more metal atoms have recently been designed. These substances occupy an intermediate position between solid state chemistry and the chemistry of metal complexes. This review presents a versatile method for synthesizing metal clusters: the reaction of complexes of transition metal halides with silylated compounds such as E(SiMe,)' (E = S, Se, Te) and E'R(SiMe3)2 (R = Ph, Me, Et; E' = P, As, Sb). Although some of the compounds thus formed have already been prepared by other routes, the method affords ready access to both small and large transition metal clusters with unusual structures and valence electron concentrations: a variety of reactions in the ligand sphere are also possible.

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“…["] If however a T H F solution of S(SiMe,), is allowed to diffuse into a T H F solution of [CpTaCI,] the salt 45 can be isolated in high yield. 44 ( Fig. 16b) The cation of 45 ( Fig.…”

Section: Clusters Of Electron-deficient Transition Metals With Cp Ligmentioning

confidence: 98%

“…Using toluene as solvent, complexes analogous to [43][44][45] are not obtained; instead, a brown compound 46 is formed exclusively. [82J (Fig.…”

Section: Clusters Of Electron-deficient Transition Metals With Cp Ligmentioning

confidence: 99%

New Transition Metal Clusters with Ligands from Main Groups Five and Six

Fenske¹,

Ohmer²,

Hachgenei³

et al. 1988

Angew. Chem. Int. Ed. Engl.

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194

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“…B. neuer magnetoresistenter Materialien, [2] sowie neuer Supraleiter [3] veröffentlicht. 1997 wurde eine Methode zur naûchemischen Herstellung von Materialbibliotheken unter Anwendung von Tintenstrahltechnologie für die Entwicklung neuer lumineszierender Materialien [4] eingesetzt. 1998 wurden dann mit kombinatorischen Methoden neue, blau photolumineszierende Materialien entdeckt.…”

Section: Ir-thermographische Erkennung Katalytischer Aktivität In Komunclassified

“…[9] Dies ist möglicherweise auch der Grund dafür, daû bei der zu Gleichung (3) analogen Umsetzung von Silberacetat, PtBu 3 und nBuSeSiMe 3 der Cluster 5 gebildet wird, der mit 3 strukturell nahezu identisch ist [Gl. (4)]. Der Unterschied zu CH 3 CO 2 Ag 3 besteht in der Zahl der an der Clusteroberfläche koordinierten Phosphanliganden.…”

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Synthesen und Strukturen der neuen Ag-Se-Cluster [Ag30Se8(SetBu)14(PnPr3)8], [Ag90Se38(SetBu)14(PEt3)22], [Ag114Se34(SenBu)46(PtBu3)14], [Ag112Se32(SenBu)48(PtBu3)12] und [Ag172Se40(SenBu)92(dppp)4]

1998

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Beachtlich erweitert wurde die Gruppe der Ag‐Se‐Cluster durch die Synthesen der Titelverbindungen – eine Bestätigung für das Konzept, durch das Anbringen von organischen Liganden an der Clusteraußenseite die Zusammenlagerung zu stabilen binären Seleniden zu vermeiden. Das als Schutzligand verwendete Phosphan hat einen großen Einfluß auf die Struktur des entstehenden Clusters. Dargestellt ist die Struktur von [Ag90Se38(SetBu)14(PEt3)22] (die tBu‐ und Et‐Gruppen sind der Übersichtlichkeit halber nicht gezeigt).

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“…Famous examples are synthetic analogues of the active sites in iron ± sulfur proteins such as [{(RS)Fe} 4 S 4 ] 2À (R cysteinyl for biological systems; R alkyl or aryl for synthetic analogues). [27] Of the multitude of further similar systems, the following compounds that are related to 5 are given as examples: [(CpCo) 4 S 4 ] n (n 0, 1), [28] [{(Ph 3 P)Co} 4 Se 4 ], [29] and [{(tBuSe)Co} 4 Se 4 ] À . [30] However, compound 5 is the first cobalt ± selenide heterocubane ligated by a Cp derivate.…”

Section: Introductionmentioning

confidence: 99%

A New Route into Single-Crystalline Partially Oxidized Cobalt Compounds: Reactions with Zintl-Type Hexaselenodistannate(III) K6Sn2Se6 as Mild Oxidant

Dehnen

Zimmermann

2000

Chem. Eur. J.

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Reactions of K6Sn2Se6 (1) with [Cp*CoCl]2 were investigated in order to probe the stability of the formal +3 oxidation state at Sn and possible ligand properties of heteroatomic zintl-type anion "Sn2Se6(6)- ". From these experiments, we obtained the following compounds that are oxidized to different extent as a result of the reaction with SnIII: [Cp2*Co][Cl2Co(mu2-Cl)2Li(thf)2] (2), [(Cp*Co)3(mu-Se)2] (3), [(Cp*Co)3(mu3-Se)2][Cl2Co(mu2-Cl)2Li(thf)2] (4), and [(Cp*Co)4(mu3-Se)4] (5). These compounds were structurally characterized by single-crystal X-ray diffractometry. It shows that the reaction conditions strongly affect the type and oxidation state of the isolated product. Two of the observed compounds, 3 and 4, are closely related both structurally and electronically; this is discussed and further illustrated by cyclovoltammetric measurements. The choice of the terminal Cp* ligand attached to the transition metal in the reactand complex is assumed to be basically dependent for the alignment of unexpected structural details when compared with known compounds of similar compositions. In conclusion, 1 is observed to act as mild oxidant as well as selenide donor, but is not in the position to keep its Sn-Se framework under the given reaction conditions.

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Neue Übergangsmetallcluster‐Komplexe mit Liganden der fünften und sechsten Hauptgruppe

Cited by 95 publications

References 185 publications

New Transition Metal Clusters with Ligands from Main Groups Five and Six

New Transition Metal Clusters with Ligands from Main Groups Five and Six

Synthesen und Strukturen der neuen Ag-Se-Cluster [Ag30Se8(SetBu)14(PnPr3)8], [Ag90Se38(SetBu)14(PEt3)22], [Ag114Se34(SenBu)46(PtBu3)14], [Ag112Se32(SenBu)48(PtBu3)12] und [Ag172Se40(SenBu)92(dppp)4]

A New Route into Single-Crystalline Partially Oxidized Cobalt Compounds: Reactions with Zintl-Type Hexaselenodistannate(III) K6Sn2Se6 as Mild Oxidant

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