Metallierung von Triisopropylsilylarsan durch Bis(tetrahydrofuran)calcium-bis[tris(trimethylsilylmethyl)zinkat]

Westerhausen, Matthias; Gückel, Christian; Piotrowski, Holger; Vogt, Martin

doi:10.1002/1521-3749(200205)628:4<735::aid-zaac735>3.0.co;2-q

Cited by 32 publications

(16 citation statements)

References 19 publications

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“…The reaction of the distilled heavy alkaline-earth metals calcium, strontium and barium with bis(trimethylsilylmethyl)zinc yielded the corresponding tris(trimethylsilylmethyl)zincates according to eqn (6). 80, 81 In these complexes the main structural fragment is the central M II ZnC 2 ring with two bridging alkyl groups. In solution only one type of alkyl group could be observed due to an exchange reaction which is fast on the NMR time scale.…”

Section: Iii2 Zincates and Cuprates Of The Heavy Alkaline-earth Metalsmentioning

confidence: 99%

Recent developments in the field of organic heterobimetallic compounds of the alkaline-earth metals

Westerhausen

2006

Dalton Trans.

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118

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Heterobimetallic compounds of the alkaline-earth metals show a wide structural variety with strongly differing reactivity patterns. The combination of magnesium and alkali metal amides yields cyclic molecules with an extreme high reactivity which often are considered as "inverse crowns" with the metal atoms as coordination sites for Lewis bases. In other metallates of the alkaline-earth metals an activation of alkyl groups succeeds. In alkaline-earth metal zincates an inverse coordination of the type M(2)[(mu-R)(2)ZnR](2) is observed and the alkyl groups are in bridging positions between zinc and the s-block metals thus forming a very reactive M-C-Zn three-center-two-electron bond. Furthermore, the metals of the carbon group form alkaline-earth metal-silicon, -germanium and -tin bonds or, in the presence of very strong Lewis bases, even solvent-separated ion pairs. For electronegative substituents at tin an inverse coordination mode such as M[(mu-R)(2)SnR](2) is observed.

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Section: Iii2 Zincates and Cuprates Of The Heavy Alkaline-earth Metalsmentioning

confidence: 99%

Recent developments in the field of organic heterobimetallic compounds of the alkaline-earth metals

Westerhausen

2006

Dalton Trans.

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118

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“…[39] Calcium readily reacts with dialkyl zinc to trialkyl zincates of the type [Ca-(ZnR 3 ) 2 ]. [40] However, the liberation of dialkyl calcium from these zincates is not possible. The transmetalation of phenylcopper yields the solvent-separated ions [(thf) 3 Ca(m-Ph) 3 Ca-(thf) 3 ] + [Ph-Cu-Ph] À with hexacoordinate calcium atoms (d(CaÀC) = 260.5(3)-262.…”

Section: Summary and Perspectivesmentioning

confidence: 99%

Aryl Calcium Compounds: Syntheses, Structures, Physical Properties, and Chemical Behavior

et al. 2007

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Organocalcium chemistry is still in its infancy. The direct synthesis of activated calcium and (substituted) iodobenzenes allows for the large-scale and high-yield synthesis of aryl calcium iodides. The influence of the substitution patterns of the phenyl group, halogen atom, and solvent is discussed. Aryl calcium iodides show a Schlenk equilibrium that enables the isolation of diaryl calcium derivatives. Owing to the high reactivity of aryl calcium halides, low temperatures have to be maintained throughout the preparative procedures in order to avoid side reactions. A decrease of reactivity and, hence, an enhanced stability at higher temperatures can be achieved by shielding of the calcium atom by increasing the coordination number of the metal center or by substitution of the iodide anion by bulky groups.

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“…Calcium reagiert bereitwillig mit Dialkylzink zu den Trialkylzinkaten des Typs [Ca(ZnR 3 ) 2 ]. [40] Eine thermische Freisetzung von Dialkylcalcium aus diesen Zinkaten ist nicht möglich. Die Transmetallierung von Phenylkupfer führt zur Bildung der lösungsmittelgetrennten Ionen [(thf) 3 Ca(m-Ph) 3 Ca(thf) 3 ] + [Ph-Cu-Ph] À mit sechsfach koordinierten Calciumatomen [d(Ca-C) = 260.5(3)-262.5(2) pm].…”

Section: Ausblickunclassified

Arylcalcium‐Verbindungen: Synthesen, Strukturen, physikalische Eigenschaften und chemisches Verhalten

et al. 2007

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Die Organocalciumchemie steht noch immer am Anfang ihrer Entwicklung. Die Direktsynthese aus Iodarenen und aktiviertem Calciumpulver eröffnet einen einfachen Zugang zu Arylcalciumiodiden in guten Ausbeuten. Der Einfluss des Substitutionsmusters der Phenylgruppe, des Halogens und des Lösungsmittels wird diskutiert. Die Arylcalciumhalogenide zeigen ein Schlenk‐Gleichgewicht, das die Isolierung von Diarylcalciumderivaten ermöglicht. Wegen der hohen Reaktivität der Arylcalciumhalogenide müssen während der Herstellung und Handhabung tiefe Temperaturen aufrechterhalten werden. Eine geringere Reaktivität und höhere Beständigkeit können durch sterisches Abschirmen des Calciumatoms erreicht werden, z. B. durch Erhöhung der Koordinationszahl des Metallzentrums oder Substitution des Iodidions durch sperrige Gruppen.

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Metallierung von Triisopropylsilylarsan durch Bis(tetrahydrofuran)calcium-bis[tris(trimethylsilylmethyl)zinkat]

Cited by 32 publications

References 19 publications

Recent developments in the field of organic heterobimetallic compounds of the alkaline-earth metals

Recent developments in the field of organic heterobimetallic compounds of the alkaline-earth metals

Aryl Calcium Compounds: Syntheses, Structures, Physical Properties, and Chemical Behavior

Arylcalcium‐Verbindungen: Synthesen, Strukturen, physikalische Eigenschaften und chemisches Verhalten

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