Recent Developments in the Chemistry of Metal Silyls of the Type M(SiR<sub>3</sub>)<sub>n</sub>

Wiberg, Egon; Stecher, Oskar; Andrascheck, H. J.; Kreuzbichler, L.; Staude, Eberhard

doi:10.1002/anie.196305071

Cited by 87 publications

(49 citation statements)

References 5 publications

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“…Conversely, C-tetrahedrane is a hypothetical compound that has not been synthesized without substituents. [93,94] For Si, just a handful of Si n R n polyhedranes, such as Si-tetrahedranes, [95,96] Si-cubanes, [97,98] and fully substituted Si-dodecahedranes [99] are experimentally available. Even less abundant are the Ge n R n cages based on Ge-tretrahedranes [100] and Ge-cubanes.…”

Section: Dimers Of Group 14 Polyhedranesmentioning

confidence: 99%

Intermolecular interactions in group 14 hydrides: Beyond CH···HC contacts

2017

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In line with previous work in which we established the factors that enhance attractive CH···HC dihydrogen interactions in alkanes, an extended theoretical analysis of noncovalent intermolecular interactions in group 14 hydrides is presented here. Remarkably, these weak interactions may play a major role in determining the crystal structures adopted by several families of molecules. A combined structural and computational analysis at the MP2 level allowed us to identify and characterize different interactions of the type EH···HE and E···HE (E = Si, Ge, Sn, and Pb), and to find also the most suitable scenario for the establishment of each particular type. The nature of the interactions has been analyzed in terms of natural charges of the atoms involved and a topological analysis of the electron density of several dimers confirms the existence of H···H and H···E attractive contacts. We have observed that the interaction strength increases when descending down the periodic group and that silicon has a marked tendency to establish Si···HSi interactions. A size‐dependent backbone effect that reinforces H···H dihydrogen interactions in polyhedral systems has also been found.

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Section: Dimers Of Group 14 Polyhedranesmentioning

confidence: 99%

Intermolecular interactions in group 14 hydrides: Beyond CH···HC contacts

2017

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“…[41] It is noteworthy that, under the same reaction conditions, neither the Er or K metals alone, nor the one generated in situ by treating K with ErCl 3 in a 3:1 ratio, underwent reductive cage opening; in both cases the closo-carborane precursor was recovered. Although the Na/Hg alloy has been widely used in coupling reactions of many organometallic species, [42] there have been no reports of its use either in the reductive cage opening of the carboranes or in the synthesis of mercuracarborane complexes. Therefore, the reaction shown in Scheme 3 is an unprecedented example of a new reductive cage-opening process that could prove applicable to the closo-carboranes in both the icosahedral and sub-icosahedral cage systems, thus affording hitherto unknown metallacarborane species.…”

Section: Reductive Cage-opening Process With Concomitant Metalation Omentioning

confidence: 99%

Recent Advances in the Chemistry of Metallacarboranes

Hosmane

Maguire

2003

Eur J Inorg Chem

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Most carborane derivatives of the icosahedral (C2B10) or small cage (C2B4) systems are formed by varying the groups on the cage carbon atoms. This is usually accomplished in the original carborane synthesis by treating substituted acetylenes with either the decaborane(14) or pentaborane(9) precursors to give directly carboranes that have adjacent carbon atoms in the cage (“carbon atoms adjacent”). The larger cages are obtained as closo‐icosahedra, while the small‐cage C2B4 carboranes have nido structures as well as a cage geometry in which the carbon atoms are separated by a boron atom. Although these “carbon atoms apart” or nido‐2,4‐(CR)2B4H6 carboranes are thermodynamically more stable and are more symmetric than the “carbon atoms adjacent” isomers, they have not been as well studied, mainly because they must be synthesized from their “carbon atoms adjacent” analogues through a sequential series of oxidative cage‐closure/reductive cage‐opening reactions. We have concentrated much of our recent research on the reactivity patterns of C(cage)‐appended alkyl‐ and silylamido, alkyloxo, alkylphosphido, and alkylthio derivatives of the “carbon atoms apart” carboranes. We have also sought to develop a safe, bench‐scale preparation of small‐cage carboranes that does not require isolating and handling dangerous and toxic carborane precursors such as pentaborane(9). This microreview discusses the latest developments towards such a process and the subsequent reaction chemistry of the “carbon atoms apart” carboranes. ((© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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“…Die Substanzen Zn(SiPh 3 ) 2 , Hg(SiMe 3 ) 2 und Hg(SiPh 3 ) 2 wurden als erste Beispiele letzterer Verbindungsklasse von Wiberg et al in den sechziger Jahren des vorigen Jahrhunderts durch Reaktion von ZnCl 2 sowie HgCl 2 mit KSiPh 3 in flu È ssigem Ammoniak bzw. durch Einwirkung von Natriumamalgam auf Me 3 SiBr erhalten [4]. Es folgten in den siebziger Jahren die Silanide Zn(SiMe 3 ) 2 und Cd(SiMe 3 ) 2 [5] sowie Cd(SitBu 3 ) 2 und Hg(SitBu 3 ) 2 [6], die Ro È sch et al durch Silylierung von MCl 2 (M = Zn Cd) mit LiAl-(SiMe 3 ) 4 sowie von MR 2 (M = Cd, Hg; R = Et, tBu) mit tBu 3 SiH erhielten.…”

Section: Introductionunclassified

Disupersilylsilanide M(SiHR2)2 der Zinkgruppenmetalle (M = Zn, Cd, Hg; R = SitBu3): Synthesen, Charakterisierung und Strukturen

Wibeŕg¹,

Niedermayer²,

Lerner³

et al. 2001

Z. anorg. allg. Chem.

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Professor Kurt Dehnicke zum 70. Geburtstag gewidmet Inhaltsu È bersicht. Bis(disupersilylsilyl)metalle M(SiHR Ã 2 ) 2 (R* = Supersilyl = SitBu 3 ) mit M = Zn, Cd, Hg bilden sich in Tetrahydrofuran/Benzol/Pentan durch Einwirkung von NaSiHR Ã 2 auf ZnCl 2 , CdI 2 , HgCl 2 im Molverha È ltnis 2 : 1. Die Verbindungen bilden farblose, in organischen Medien lo È sliche, nicht hydrolyse-und luftempfindliche Kristalle, deren Thermolyse-und Photolysestabilita È t in der Reihe Zn > Hg > Cd-Verbindung abnimmt. Gema Èû Ro È ntgenstrukturanalysen sind die Verbindungen M(SiHR Ã 2 ) 2 monomer mit einem ± bisher nicht beobachteten ± gewinkelten Geru È st ±M± (Winkel SiMSi fu È r M(SiHR Ã 2 ) 2 mit M = Zn/Cd/Hg 170.7/174.2/174.4°).Disupersilylsilanides M(SiHR Ã 2 ) 2 of Metals of the Zinc Group (M = Zn, Cd, Hg; R* = SitBu 3 ): Syntheses, Characterization, and Structures Abstract. Bis(disupersilyl)silylmetals M(SiHR Ã 2 ) 2 (R* = Supersilyl = SitBu 3 ) with M = Zn, Cd, Hg are obtained in tetrahydrofuran/benzene/pentane by the reaction of NaSiHR Ã 2with ZnCl 2 , CdI 2 , HgCl 2 in the molar ratio 2 : 1. The compounds form colorless, in organic media soluble, not hydrolysis-and air-sensitive crystals, the stabilities of which for thermolysis or photolysis decrease in the row Zn > Hg > Cd compound. According to X-ray structure analyses, the compounds M(SiHR Ã 2 ) 2 are monomeric with a ± to date not observed ± non-linear framework ±M± (angle SiMSi for M(SiHR Ã 2 ) 2 with M = Zn/Cd/Hg 170.7/174.2/174.4°).

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Recent Developments in the Chemistry of Metal Silyls of the Type M(SiR₃)_n

Cited by 87 publications

References 5 publications

Intermolecular interactions in group 14 hydrides: Beyond CH···HC contacts

Intermolecular interactions in group 14 hydrides: Beyond CH···HC contacts

Recent Advances in the Chemistry of Metallacarboranes

Disupersilylsilanide M(SiHR2)2 der Zinkgruppenmetalle (M = Zn, Cd, Hg; R = SitBu3): Synthesen, Charakterisierung und Strukturen

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Recent Developments in the Chemistry of Metal Silyls of the Type M(SiR3)n

Cited by 87 publications

References 5 publications

Intermolecular interactions in group 14 hydrides: Beyond CH···HC contacts

Intermolecular interactions in group 14 hydrides: Beyond CH···HC contacts

Recent Advances in the Chemistry of Metallacarboranes

Disupersilylsilanide M(SiHR*2)2 der Zinkgruppenmetalle (M = Zn, Cd, Hg; R* = SitBu3): Synthesen, Charakterisierung und Strukturen

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Product

Resources

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Recent Developments in the Chemistry of Metal Silyls of the Type M(SiR₃)_n

Disupersilylsilanide M(SiHR2)2 der Zinkgruppenmetalle (M = Zn, Cd, Hg; R = SitBu3): Synthesen, Charakterisierung und Strukturen