Oligomeric Solvent-Free Magnesium Bis(phosphanides) − Molecular Structure of Trimeric Magnesium Bis[bis(trimethylsilyl)phosphanide]

Westerhausen, Matthias; Digeser, Matthias H.; Wieneke, Birgit; Nöth, Heinrich; Knizek, Jörg

doi:10.1002/(sici)1099-0682(199804)1998:4<517::aid-ejic517>3.0.co;2-d

Cited by 27 publications

(11 citation statements)

References 17 publications

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“…This can be traced back to the different coordination numbers of the phosphorus atoms (four in the inner ring and three outside the inner ring). Similar bond lengths could also be found in other magnesium phosphanides; for example for the bicyclic species [Mg 3 {P(SiMe 3 ) 2 } 6 ] the distances are between 245 and 262 pm 6. Compound 2 is not soluble in non‐ or weakly polar solvents (e.g.…”

Section: Synthesis and Characterisationsupporting

confidence: 64%

Observation and Interpretation of Structural Variety in Alkaline Earth Metal Derivatives of Diphosphanyldisiloxane

et al. 2010

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Alkaline earth metal derivatives of the diphosphanyldisiloxane O(SiiPr 2 PH 2 ) 2 (1) were obtained by reactions of 1 with MgBu 2 and M{N(SiMe 3 ) 2 } 2 (M = Ca, Sr, Ba), respectively. The metal complexes formed were characterised by elemental analysis, NMR spectroscopy, and IR spectroscopy as well as by single-crystal structure analysis. The solid-state structures depend on the metal ion involved. The magnesium derivative crystallizes from thf as a trimer and exhibits a six-mem-

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Section: Synthesis and Characterisationsupporting

confidence: 64%

Observation and Interpretation of Structural Variety in Alkaline Earth Metal Derivatives of Diphosphanyldisiloxane

et al. 2010

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“…The Mg–P bond lengths of 6a (2.7001(10), 2.6931(10) Å) are significantly longer than that of the related magnesium phosphide complex [(BDI)Mg(PPh 2 )·THF] (Mg–P = 2.531 Å) . All other reported terminal magnesium phosphide complexes also display relatively short Mg–P distances and involve the primary phosphide anion [HPPh] − (Mg–P = 2.550–2.593 Å) , or the bulky secondary phosphide [P(SiMe 3 ) 2 ] − (Mg–P = 2.450–2.502 Å). − This effect can be rationalized by the presence of a BH 3 group, which denudes the Lewis basicity of the already soft phosphorus donor toward magnesium. Although the structure is noncentrosymmetric, the dimer is propagated through two agostic-type B–H–Mg interactions per boron.…”

Section: Resultsmentioning

confidence: 99%

Alkaline-Earth Derivatives of Diphenylphosphine–Borane

et al. 2020

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Treatment of β-diketiminato (BDI = HC{C(CH 3 )Ndipp)} 2 where dipp = 2,6-iPr 2 C 6 H 3 ) magnesium butyl [(BDI)MgBu] (I) and calcium hexamethyldisilazide [(BDI)Ca{N(SiMe 3 ) 2 }] (II) complexes with equimolar quantities of diphenylphosphine− borane, Ph 2 PH•BH 3 , results in the formation of the respective alkaline earth (Ae) phosphidoborane derivatives [(BDI)Mg(Ph 2 PBH 3 )] 2 (6a) and [(BDI)Ca(Ph 2 PBH 3 )] (7a). Although satisfactory single crystals of 7a could not be obtained, 6a was crystallographically characterized and both compounds display similar NMR spectra. The dimeric Ae-hydride complexes [(BDI)AeH] 2 (IIIa, Ae = Mg; IIIb, Ae = Ca) react with substoichiometric quantities of Ph 2 PH•BH 3 , allowing the crystallization of the dimeric Mg and trimeric Ca phosphidoborane species [(BDI)Mg(H)(H 3 BPPh 2 )Mg(BDI)] (8) and [{(BDI)Ca} 3 (H)-(H 3 BPPh 2 ) 2 ] (9). In the absence of coordinating Lewis bases, compounds 6a, 7a, 8, and 9 display dynamic solution-state behavior (in benzene and toluene), while addition of THF furnishes the monomeric adducts [(BDI)Mg(H 3 BPPh 2 )•THF] (6b) and [(BDI)Ca-(H 3 BPPh 2 )•THF] (7b). Addition of Ph 2 PH•BH 3 to compound 6a results in BH 3 transfer to eliminate Ph 2 PH and generate the phosphinodiboronate complex [(BDI)Mg{(H 3 B) 2 PPh 2 }] 2 (10) in preference to dehydrocoupling of the phosphidoborane and phosphine−borane reagents.Article pubs.acs.org/Organometallics

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“…Ausgewa È hlte Bindungsla È ngen und -winkel sind in Tabelle 2 aufgelistet. Drei in Reihe angeordnete Erdalkalimetallzentren sind in der Phosphanidchemie ungewo È hnlich und wurden bisher nur bei dem trimeren Magnesium-bis[bis(trimethylsilyl)phosphanid] beobachtet[12].Die Bis(trimethylsilyl)amid-Substituenten weisen trigonal planar koordinierte Stickstoffatome auf. Der groûe Si±N±Si-Winkel beruht auf sterischer Abstoûung zwischen den Trimethylsilylgruppen[13].…”

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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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Oligomeric Solvent-Free Magnesium Bis(phosphanides) − Molecular Structure of Trimeric Magnesium Bis[bis(trimethylsilyl)phosphanide]

Cited by 27 publications

References 17 publications

Observation and Interpretation of Structural Variety in Alkaline Earth Metal Derivatives of Diphosphanyldisiloxane

Observation and Interpretation of Structural Variety in Alkaline Earth Metal Derivatives of Diphosphanyldisiloxane

Alkaline-Earth Derivatives of Diphenylphosphine–Borane

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

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