Benzene-Centered Tri- and Tetrametallacarborane Sandwich Complexes

Bluhm, Martin E.; Pritzkow, Hans; Siebert, Walter; Grimes, Russell N.

doi:10.1002/1521-3773(20001215)39:24<4562::aid-anie4562>3.0.co;2-8

Cited by 29 publications

(3 citation statements)

References 25 publications

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“…Cs 2 [B 10 Br 10 ]´2 H 2 O crystallizes monoclinic (space group I2/a, (no. 15), Z = 8, a = 1361.54 (9) pm, b = 1215.89 (5) pm, c = 3108.4(2) pm, a = 90°, b = 97.916(8)°, c = 90°). The closo-cluster B 10 Br 10 2± has a bicapped square antiprismatic structure with idealized D 4d symmetry.…”

Section: Professor Ekkehard Fluck Zum 70 Geburtstag Gewidmetmentioning

confidence: 99%

Chemische und cyclovoltammetrische Untersuchung der Redoxreaktionen der Decahalogendecaboratecloso-[B10X10]2- undhypercloso-[B10X10]· - (X = Cl, Br). Kristallstrukturanalyse von Cs2[B10Br10] · 2 H2O

Einholz¹,

Vaas²,

Wieloch³

et al. 2002

Z. anorg. allg. Chem.

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Professor Ekkehard Fluck zum 70. Geburtstag gewidmet Inhaltsu È bersicht. Die Oxidation der Decachlor-closodecaborate(2±) Cs 2 [B 10 Cl 10 ] oder [Me 4 N] 2 [B 10 Cl 10 ] mit Tl(CF 3 COO) 3 ergibt das Radikal-Monoanion hypercloso-[B 10 Cl 10 ]´±, das durch ESR-und UV/Vis-Spektroskopie charakterisiert wurde. [B 10 Cl 10 ]´± dimerisiert nicht wie [B 10 H 10 ]´±, es wird aber durch Acetonitril zum Dianion [B 10 Cl 10 ] 2± reduziert. Cs 2 [B 10 Cl 10 ] reagiert mit sta È rkeren Oxidationsmitteln wie CoF 3 (in Dichlormethan) oder XeF 2 (in Perfluorhexan) unter Bildung von B 9 Cl 9 und ± in Spuren ± B 8 Cl 8 . Im Gegensatz zu diesen Befunden zeigt der Decabrom-closo-decaborat-Cluster Cs 2 [B 10 Br 10 ] keine Reaktionen mit Tl(CF 3 COO) 3 in Acetonitril oder mit CoF 3 in CH 2 Cl 2 . Die Oxidation der Dianionen [B 10 X 10 ] 2± (X = Cl, Br) wurde durch elektroanalytische Methoden (Cyclovoltammetrie, Chronoamperometrie, Chronocoulometrie) untersucht. Fu È r die zwei Stufen der Reaktion wurden die Formalpotentiale bestimmt, die keinen Einfluû von Struktura È nderungen erkennen lassen. Die Struktur von Cs 2 [B 10 Br 10 ]´2 H 2 O wurde an einem Einkristall durch Ro È ntgendiffraktometrie bestimmt. Cs 2 [B 10 Br 10 ]2 H 2 O kristallisiert monoklin (Raumgruppe I 2/a (Nr. 15), Z = 8, a = 1361,54(9) pm, b = 1215,89(5) pm, c = 3108,4(2) pm, a = 90°, b = 97,916(8)°, c = 90°). Der closo-Cluster [B 10 Br 10 ] 2± hat die Struktur des zweifach u È berkappten quadratischen Antiprismas mit idealisierter D 4d -Symmetrie. Chemical and Cyclovoltammetric Investigation of the Redoxreactions of the Decahalodecaborates closo-[B 10 X 10 ] 2± and hypercloso-[B 10 X 10 ]´± (X = Cl, Br) 1) . Crystal Structure Analysis of Cs 2 [B 10 Br 10 ]´2 H 2 O Abstract. The oxidation of the decachloro-closo-decaborates(2±) Cs 2 [B 10 Cl 10 ] or [Me 4 N] 2 [B 10 Cl 10 ] with Tl(CF 3 COO) 3 leads to the corresponding radical monoanion hypercloso-[B 10 Cl 10 ]´±, which was characterized by ESR and UV/Vis spectroscopy. [B 10 Cl 10 ]´± does not dimerize like [B 10 H 10 ]´± but it is reduced by acetonitrile to the dianion [B 10 Cl 10 ] 2± . Cs 2 [B 10 Cl 10 ] reacts with stronger oxidation agents like CoF 3 (in dichloromethane) or XeF 2 (in perfluorhexane), respectively, to yield B 9 Cl 9 and, in traces, B 8 Cl 8 . In opposite to this, the decabromoderivative Cs 2 [B 10 Br 10 ] does not show any reaction with Tl(CF 3 COO) 3 in acetonitrile or with CoF 3 in CH 2 Cl 2 .The oxidation of the dianions [B 10 X 10 ] 2± (X = Cl, Br) was studied by electroanalytical methods (cyclic voltammetry, chronoamperometry, chronocoulometry). Formal potentials were determined for the two steps of the reaction, which do not seem to be affected by structural rearrangements.The crystal structure of Cs 2 [B 10 Br 10 ]´2 H 2 O was analyzed by single-crystal X-ray diffraction. Cs 2 [B 10 Br 10 ]´2 H 2 O crystallizes monoclinic (space group I2/a, (no. 15), Z = 8, a = 1361.54(9) pm, b = 1215.89(5) pm, c = 3108.4(2) pm, a = 90°, b = 97.916(8)°, c = 90°). The closo-cluster B 10 Br 10 2± has a bi...

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Section: Professor Ekkehard Fluck Zum 70 Geburtstag Gewidmetmentioning

confidence: 99%

Chemische und cyclovoltammetrische Untersuchung der Redoxreaktionen der Decahalogendecaboratecloso-[B10X10]2- undhypercloso-[B10X10]· - (X = Cl, Br). Kristallstrukturanalyse von Cs2[B10Br10] · 2 H2O

Einholz¹,

Vaas²,

Wieloch³

et al. 2002

Z. anorg. allg. Chem.

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“…This analogy provides a mechanism to predict new, hopefully stable, molecules and to compare molecular fragments with each other and with familiar species from organic chemistry and also offers clues about reactivity and reaction mechanisms. The boron connection is an attempt to map the structural chemistry of boranes and carboranes [26-31] to the structural chemistry of silicon [32] and silicon-carbon clusters, respectively. Boranes and carboranes constitute a very rich and well-established branch of chemistry with well-known structural and stability rules and powerful concepts [26-30].…”

Section: Introductionmentioning

confidence: 99%

“…Boranes and carboranes constitute a very rich and well-established branch of chemistry with well-known structural and stability rules and powerful concepts [26-30]. Since boranes and borane-based molecular fragments and nano composites - including carboranes, bisboranes and metallaboranes - and metallacarboranes are very well studied [26-31,33-35] and are very well known species with many technological, chemical and biomedical [33,34] applications, their silicon, silicon-carbon (and other group 14, and 15) analogues [35,36] are expected to be very important and very promising for analogous applications.…”

Section: Introductionmentioning

confidence: 99%

Designing novel Sn-Bi, Si-C and Ge-C nanostructures, using simple theoretical chemical similarities

Zdetsis

2011

Nanoscale Res Lett

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A framework of simple, transparent and powerful concepts is presented which is based on isoelectronic (or isovalent) principles, analogies, regularities and similarities. These analogies could be considered as conceptual extensions of the periodical table of the elements, assuming that two atoms or molecules having the same number of valence electrons would be expected to have similar or homologous properties. In addition, such similar moieties should be able, in principle, to replace each other in more complex structures and nanocomposites. This is only partly true and only occurs under certain conditions which are investigated and reviewed here. When successful, these concepts are very powerful and transparent, leading to a large variety of nanomaterials based on Si and other group 14 elements, similar to well known and well studied analogous materials based on boron and carbon. Such nanomaterias designed in silico include, among many others, Si-C, Sn-Bi, Si-C and Ge-C clusters, rings, nanowheels, nanorodes, nanocages and multidecker sandwiches, as well as silicon planar rings and fullerenes similar to the analogous sp2 bonding carbon structures. It is shown that this pedagogically simple and transparent framework can lead to an endless variety of novel and functional nanomaterials with important potential applications in nanotechnology, nanomedicine and nanobiology. Some of the so called predicted structures have been already synthesized, not necessarily with the same rational and motivation. Finally, it is anticipated that such powerful and transparent rules and analogies, in addition to their predictive power, could also lead to far-reaching interpretations and a deeper understanding of already known results and information.

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Boron: Organoboranes

Jï¿1⁄2ï¿1⁄2kle¹

2005

Encyclopedia of Inorganic Chemistry

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This chapter provides an overview of recent developments in the highly interdisciplinary field of organoboron chemistry. The most important routes for the synthesis of organoboranes via transmetallation, hydroboration and other boration reactions, as well as CH activation are outlined. The various classes of organoboranes thus accessible are presented according to the nature of the organic substituents. Special emphasis is given to applications of organoboranes. For example, the development of new chiral organoboranes that are commonly used in enantioselective synthesis is shown. Moreover, the importance of fluorinated arylboranes as highly efficient Lewis acid catalysts and cocatalysts for organic transformations and polymerization reactions is discussed. The use of triarylboranes and related compounds as electronic and optical materials for device applications, and as sensors for the recognition of anions and neutral Lewis bases is also described in detail.

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Benzene-Centered Tri- and Tetrametallacarborane Sandwich Complexes

Cited by 29 publications

References 25 publications

Chemische und cyclovoltammetrische Untersuchung der Redoxreaktionen der Decahalogendecaboratecloso-[B10X10]2- undhypercloso-[B10X10]· - (X = Cl, Br). Kristallstrukturanalyse von Cs2[B10Br10] · 2 H2O

Chemische und cyclovoltammetrische Untersuchung der Redoxreaktionen der Decahalogendecaboratecloso-[B10X10]2- undhypercloso-[B10X10]· - (X = Cl, Br). Kristallstrukturanalyse von Cs2[B10Br10] · 2 H2O

Designing novel Sn-Bi, Si-C and Ge-C nanostructures, using simple theoretical chemical similarities

Boron: Organoboranes

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