Synthesis and Homomolecular Metalation of Trialkylsilylphosphanides of Calcium and Barium

Westerhausen, Matthias; Digeser, Matthias H.; Krofta, Mathias; Wibeŕg, Nils; Nöth, Heinrich; Knizek, Jörg; Ponikwar, Werner; Seifert, Thomas

doi:10.1002/(sici)1099-0682(199905)1999:5<743::aid-ejic743>3.3.co;2-t

Cited by 30 publications

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“…The addition of tris(trimethylsilylmethyl)alane and unsolvated calcium bis[bis(trimethylsilyl)amide] in a 2:1 molar ratio in toluene affords the dimeric calcium bis(trimethylsilyl)amide-tetrakis(trimethylsilylmethyl) aluminate (10; Figure 7). [43] The central Ca 2 N 2 core of the complex is planar. The complex exhibits calcium-carbon distances of 2.68 and 2.64 Å .…”

Section: ''Ate'' Complexes Of Calcium Strontium and Bariumsupporting

confidence: 89%

Not Just Heavy “Grignards”: Recent Advances in the Organometallic Chemistry of the Alkaline Earth Metals Calcium, Strontium and Barium

Alexander

Ruhlandt‐Senge

2002

Eur. J. Inorg. Chem.

146

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Section: ''Ate'' Complexes Of Calcium Strontium and Bariumsupporting

confidence: 89%

Not Just Heavy “Grignards”: Recent Advances in the Organometallic Chemistry of the Alkaline Earth Metals Calcium, Strontium and Barium

Alexander

Ruhlandt‐Senge

2002

Eur. J. Inorg. Chem.

146

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“…Bei der stufenweisen Metallierung dieser prima È ren Phosphane mit M[N(SiMe 3 ) 2 ] 2 lieûen sich bisher die Verbindungen mit einem Amid/Phosphanid-Verha È ltnis von 1/1 [1,5,9,10] …”

Section: Introductionunclassified

Synthese eines hexanuklearen Calcium–Phosphor-Käfigs über heteroleptische Calcium-amid-phosphanid-Vorstufen

Westerhausen

Krofta

Mayer

2000

Z. anorg. allg. Chem.

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Inhaltsu È bersicht. Nach der Metallierung von Tri(tert-butyl)silylphosphan mit Calcium-bis[bis(trimethylsilyl)amid] isoliert man das Dimer {(Me 3 Si) 2 N±Ca(THF)[l-P(H)-Si t Bu 3 ]} 2 (1). Die in THF-Lo È sung auftretende Monomerisierung und anschlieûend einsetzende Dismutierung fu È hrt zu den homoleptischen Verbindungen (THF) 2 Ca[N(SiMe 3 ) 2 ] 2 und (THF) 4 Ca[P(H)Si t Bu 3 ] 2 . Bei der in Toluol beobachteten Dismutierungsreaktion wird Bis(tetrahydrofuran)calciumbis[bis(trimethylsilyl)amid] zuru È ckgewonnen und kristallines [(Me 3 Si) 2 N±Ca(THF)] 2 Ca[P(H)Si t Bu 3 ] 4 (2) scheidet sich ab. Bei erho È hter Temperatur eliminiert 2 zwei Øquivalente HN(SiMe 3 ) 2 und dimerisiert. Die Ka È figverbindung (THF) 2 Ca 6 [PSi t Bu 3 ] 4 [P(H)Si t Bu 3 ] 4 (3) mit einem zentralen Ca 4 P 4 -Heterocubanfragment kristallisiert beim Ku È hlen der Reaktionslo È sung. Die Moleku È lstrukturen von 2 und 3 wurden ro È ntgenographisch ermittelt. Abstract. The metalation of tri(tert-butyl)silylphosphane with calcium bis[bis(trimethylsilyl)amide] yields the dimer {(Me 3 Si) 2 N±Ca(THF)[l-P(H)Si t Bu 3 ]} 2 (1). In THF monomerization occurs and dismutation reactions lead to the homoleptic compounds, namely (THF) 2 Ca[N(SiMe 3 ) 2 ] 2 and (THF) 4 Ca[P(H)Si t Bu 3 ] 2 . In toluene, 1 undergoes dismutation reactions, bis(tetrahydrofuran)calcium bis[bis(trimethylsilyl)amide] is regained and [(Me 3 Si) 2 N±Ca(THF)] 2 Ca[P(H)-Si t Bu 3 ] 4 (2) precipitates. At raised temperatures, 2 undergoes a homometallic metalation with the loss of two equivalents of HN(SiMe 3 ) 2 and dimerizes. The thus formed cage compound (THF) 2 Ca 6 [PSi t Bu 3 ] 4 [P(H)Si t Bu 3 ] 4 (3) with a central Ca 4 P 4 heterocubane moiety crystallizes upon cooling of the toluene solution. The molecular structures of 2 and 3 were determined.

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“…This fact leads to broadened resonances (1a and 1b) or a doubling of the signals (2a and 2b). Similar monomerϪdimer equilibria are well-known in the chemistry of alkaline earth metal bis(phosphanides) [13] Ϫ strontium- [14] and barium bis(triisopropylsilylphosphanide) [15] show this equilibrium even in donor solvents such as THF. Scheme 2.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of 2,2′,5,5′-Tetraphenyl-1,1′-diarsacalcocene and -strontocene

Westerhausen

Birg

Piotrowski

2000

Eur. J. Inorg. Chem.

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The metalation of H2As−SiiPr3 with bis(tetrahydrofuran‐O)calcium‐ and ‐strontium bis[bis(trimethylsilyl)amide] yields tetrakis(tetrahydrofuran‐O)calcium‐ (1a) and ‐strontium bis(triisopropylsilylarsanide) (2a). These compounds are in equilibrium with their dimers 1b (Ca) and 2b (Sr) by elimination of THF. The addition of diphenylbutadiyne to a THF/toluene solution of 1 and 2 gives bis(tetrahydrofuran‐O)calcium‐ (3) and ‐strontium bis(2,5‐diphenylarsolide) (4). The proposed reaction mechanism explains the formation of the (iPr3Si)2As− and 2,5‐diphenyl‐3,4‐bis(phenylethynyl)arsolide anions based on an intermolecular H/SiiPr3 exchange reaction. The latter anion was characterized by X‐ray crystallography with the binuclear cation [(THF)3Ca{µ‐As(H)SiiPr3}3Ca(THF)3]+ (5). The arsolide ligands of 3 and 4 are η5‐bonded to the metal centers, whereas 5 crystallizes as a solvent‐separated ion pair.

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Synthesis and Homomolecular Metalation of Trialkylsilylphosphanides of Calcium and Barium

Cited by 30 publications

References 0 publications

Not Just Heavy “Grignards”: Recent Advances in the Organometallic Chemistry of the Alkaline Earth Metals Calcium, Strontium and Barium

Not Just Heavy “Grignards”: Recent Advances in the Organometallic Chemistry of the Alkaline Earth Metals Calcium, Strontium and Barium

Synthese eines hexanuklearen Calcium–Phosphor-Käfigs über heteroleptische Calcium-amid-phosphanid-Vorstufen

Synthesis of 2,2′,5,5′-Tetraphenyl-1,1′-diarsacalcocene and -strontocene

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