Lithium-, Natrium- und Kupfer(I)-supersilylphosphandiide M2PSitBu3: Verbindungen mit neuartigen sphärischen (M2P)n-Gerüsten

Wibeŕg, Nils; Wörner, Angelika; Fenske, Dieter; Nöth, Heinrich; Knizek, Jörg; Polborn, Kurt

doi:10.1002/(sici)1521-3757(20000515)112:10<1908::aid-ange1908>3.0.co;2-c

Cited by 20 publications

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“…Zu den gängigen Verfahren zählt die Deprotonierung primärer Phosphane durch stark basische metallorganische Verbindungen der Alkalimetalle, wobei auch zweifache Deprotonierung möglich ist. So bilden insbesondere primäre Silylphosphane mit sterisch anspruchsvollen Organosilyl‐Gruppen bei zweifacher Deprotonierung Phosphandiide, die im Festkörper als Alkalimetall‐Phosphor‐Cluster mit sphärischen Lithium‐Phosphor‐Gerüsten vorliegen 10. Hingegen sind in Lithiumphosphaniden im Festkörper M‐P‐Einheiten zu Dimeren und Oligomeren mit Leiterstruktur,11 aber auch zu polymeren Ketten oder Helices verknüpft;12 vereinzelt liegen auch komplexere Aggregate vor 13…”

Section: Methodsunclassified

Stannaborate Transition Metal Chemistry: Ligand Properties, Reactivity, and Density Functional Theory Calculations of Platinum and Palladium Complexes

et al. 2001

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Three stannaborate complexes of platinum(II) and a novel stannoborate palladium(II) derivative have been prepared in excellent yield. The tin transition metal bond is formed through nucleophilic substitution and the resulting complexes [Bu3MeN] [trans-[(Et3P)2Pt(SnB11H11)H]] (6), [trans-[(Et3P)2Pt(SnB11H11)(CNtBu)]] (7), [Bu3MeN]2[trans-[(Et3P)2Pt(SnB11H11)2-(CNtBu)]] (8), and [Bu3MeN][(dppe)-Pd(SnB11H11)Me] (12) (dppe = 1,2-bis-(diphenylphosphanyl)ethane) were characterized by NMR spectroscopy and elemental analysis. In the cases of the zwitterion 7, the pentacoordinated complex 9, the palladium salt 12 and [(triphos)Pt(SnB11H11)] (10) (triphos = 1,1,1-tris(diphenylphosphanylmethyl)ethane), their solid-state structures are determined by X-ray crystal structure analyses. The trans influence of the [SnB11H11] ligand is evaluated from the results of the IR spectroscopy and X-ray crystallographic structures of complexes 6, 7, and 12. The dipole moment of the zwitterion 7 is calculated by density functional theory (DFT) methods. The alignment of the dipole moments of the polar molecules 7 and 12 in the solid state is discussed.

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Section: Methodsunclassified

Stannaborate Transition Metal Chemistry: Ligand Properties, Reactivity, and Density Functional Theory Calculations of Platinum and Palladium Complexes

et al. 2001

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“…These cage compounds are the first examples of a metal-centered alkali metal phosphanediide. The alkaline earth metal-free alkali metal phosphanediides tend to form spherical cages that can be oxygen-centered , or can show a metal deficiency such as in {[Li 2 PSi- i- Pr 3 ] 8 [PSi- i- Pr 3 ] 2 } …”

Section: Discussionmentioning

confidence: 99%

Cage Compounds of Heterotrimetallic Mixed Phosphanediide/Silanolate Aggregates with an Alkaline Earth Metal-Centered Phosphorus Octahedron

et al. 2002

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The lithiation of potassium triisopropylsilylphosphanide yields the corresponding phosphanediide. The subsequent metathesis reaction with SrI(2) and BaI(2) in the presence of hexamethyldisiloxane gives hexalithium hexapotassium strontium hexakis(triisopropylsilylphosphanediide)bis(trimethylsilanolate) (1) and the corresponding barium derivative (2), respectively. The alkaline earth metal atoms are surrounded octahedrally by the phosphanediide ligands. Six P(3) faces of the octahedron are capped by the K atoms, and the P-P edges of two opposite P(3) faces are bridged by the lithium atoms. The Li cations are also bonded to the Me(3)SiO substituents giving a coordination number of three for the alkali metals.

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“…This forces are overcome by the steric pressure of the tri( tert -butyl)silyl substituents favoring small aggregation grades and, furthermore, the bridging phosphanide ligands stabilizing this cation arrangement. In principle, the formal substitution of a t Bu 3 SiP(H)Mg + moiety by a monovalent cation such as Na + , K + , or Cu + seems to be possible; however, due to the loss of shielding groups a higher aggregation grade is realized in the solid state …”

Section: Discussionmentioning

confidence: 99%

Polyhedral Members of the Mg₂_nP₂_m Family Derived from Dimeric Magnesium Trialkylsilylphosphandiide

et al. 2000

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The magnesiation of tri(tert-butyl)silylphosphane in THF yields tetrameric (tetrahydrofuran-O)magnesium tri(tert-butyl)silylphosphandiide 1. The central moiety is a slightly distorted Mg4P4 cube with tetracoordinate magnesium and phosphorus atoms. The reaction of dibutylmagnesium with H2PSitBu3 in toluene gives tetramagnesium tetrakis[mu-tri(tert-butyl)silylphosphanide] bis[mu 4-tri(tert-butyl)silylphosphandiide] 2. The central fragment is a Mg4P2 octahedron with the phosphorus atoms in a trans position. The Mg...Mg edges are bridged by the phosphanide substituents. Crystallographic data of 1: C68H148Mg4O5P4Si4, monoclinic, P2(1)/c, a = 13.454(1) A, b = 26.123(1) A, c = 24.539(2) A, beta = 96.53(1) degrees, Z = 4; crystallographic data of 2: C72H166Mg4P6Si6, monoclinic, P2(1)/n, a = 13.951(1) A, b = 14.269(1) A, c = 24.209(2) A, beta = 102.415(1) degrees, Z = 2.

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Lithium-, Natrium- und Kupfer(I)-supersilylphosphandiide M2PSitBu3: Verbindungen mit neuartigen sphärischen (M2P)n-Gerüsten

Abstract: Ein „ungefülltes”︁ Dialkalimetallphosphandiid [Na2PR]6⋅2 THF mit einem Na:P‐Verhältnis von 2:1 konnte erstmals synthetisiert werden (R=SitBu3; siehe Struktur). Sphärische Gerüste weisen auch die Phosphandiide [Li2PR]4⋅4 LiOtBu und [Cu2PR]6 auf.

Cited by 20 publications

References 34 publications

Stannaborate Transition Metal Chemistry: Ligand Properties, Reactivity, and Density Functional Theory Calculations of Platinum and Palladium Complexes

Stannaborate Transition Metal Chemistry: Ligand Properties, Reactivity, and Density Functional Theory Calculations of Platinum and Palladium Complexes

Cage Compounds of Heterotrimetallic Mixed Phosphanediide/Silanolate Aggregates with an Alkaline Earth Metal-Centered Phosphorus Octahedron

Polyhedral Members of the Mg₂_nP₂_m Family Derived from Dimeric Magnesium Trialkylsilylphosphandiide

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Lithium-, Natrium- und Kupfer(I)-supersilylphosphandiide M2PSitBu3: Verbindungen mit neuartigen sphärischen (M2P)n-Gerüsten

Abstract: Ein „ungefülltes”︁ Dialkalimetallphosphandiid [Na2PR*]6⋅2 THF mit einem Na:P‐Verhältnis von 2:1 konnte erstmals synthetisiert werden (R*=SitBu3; siehe Struktur). Sphärische Gerüste weisen auch die Phosphandiide [Li2PR*]4⋅4 LiOtBu und [Cu2PR*]6 auf.

Cited by 20 publications

References 34 publications

Stannaborate Transition Metal Chemistry: Ligand Properties, Reactivity, and Density Functional Theory Calculations of Platinum and Palladium Complexes

Stannaborate Transition Metal Chemistry: Ligand Properties, Reactivity, and Density Functional Theory Calculations of Platinum and Palladium Complexes

Cage Compounds of Heterotrimetallic Mixed Phosphanediide/Silanolate Aggregates with an Alkaline Earth Metal-Centered Phosphorus Octahedron

Polyhedral Members of the Mg2nP2m Family Derived from Dimeric Magnesium Trialkylsilylphosphandiide

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Abstract: Ein „ungefülltes”︁ Dialkalimetallphosphandiid [Na2PR]6⋅2 THF mit einem Na:P‐Verhältnis von 2:1 konnte erstmals synthetisiert werden (R=SitBu3; siehe Struktur). Sphärische Gerüste weisen auch die Phosphandiide [Li2PR]4⋅4 LiOtBu und [Cu2PR]6 auf.

Polyhedral Members of the Mg₂_nP₂_m Family Derived from Dimeric Magnesium Trialkylsilylphosphandiide