Reaktionen von LiNPPh3 mit den Cyclooctatetraenid-Komplexen [Ln(C8H8)Cl(THF)2]2 von Cer und Samarium. Die Kristallstrukturen von [LiNPPh3]6, [Ln(C8H8)Li3Cl2(NPPh3)2(THF)3] (Ln = Ce, Sm) und [Li(THF)4][Sm(C8H8)2]

Anfang, S.; Seybert, Gert; Harms, Klaus; Geiseler, Gertraud; Massa, Werner; Dehnicke, Kurt

doi:10.1002/(sici)1521-3749(199807)624:7<1187::aid-zaac1187>3.0.co;2-1

Cited by 33 publications

(28 citation statements)

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“…The compound 130 was made by reacting (C 8 H 8 )SmI(THF) with the potassium salt of the diisopropyl-substituted aminotroponiminato ligand. 250 Unusual heterocubane structures containing a (C 8 H 8 )Ln unit have been reported by Dehnicke et al 251 LiNPPh 3 was found to react with the chlorobridged dimers [(C 8 H 8 )Ln(µ-Cl)(THF) 2 ] 2 (Ln ) Ce, Sm) in THF solution to give the bimetallic phosphiniminato complexes (C 8 H 8 )LnLi 3 Cl 2 (NPPh 3 ) 2 (THF) 3 (Ln ) Ce (orange), Sm (131, red)). The proposed reaction leading to the formation of these unexpected products is outlined in eq 82.…”

Section: Trivalent Lanthanide Derivativesmentioning

confidence: 79%

Synthesis and Structural Chemistry of Non-Cyclopentadienyl Organolanthanide Complexes

2002

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Over the years one major challenge has remained in organolanthanide chemistry: the synthesis of homoleptic alkyl and aryl complexes. The simplest organometallic compounds of the rare earths are the species LnR 2 or LnR 3 with the rare earth metals in their common oxidation states Ln 2+ and Ln 3+ which imply the coordination of only two or three ligands to the metal center. This is usually insufficient to meet the lanthanides' demands of steric saturation through high coordination numbers.Hence for a long time, only indirect evidence could be found for the existence of simple homoleptic organolanthanide compounds; the isolation and characterization of compounds belonging to this class were first achieved recently using pentafluorophenyl for Ln 2+ derivatives 12 and very bulky alkyl ligands for Ln 3+ species. [13][14][15] Especially for alkyls, very little structural data are available for compounds without any trimethylsilyl-substituted ligands which generally ensure higher stability. But nevertheless, due to the difficulties of their synthesis and their high reactivity alkyls and aryls still represent an interesting class of compounds. 16 Homoleptic σ-Alkyl ComplexesShortly after the synthesis of the first divalent solvent-free Ln alkyl, [(Me 3 Si) 3 C] 2 Yb, 17 the Eu analogue was prepared similarly by the reaction of EuI 2 and KC(SiMe 3 ) 3 in benzene. 18 It also features the bent structure displayed by the Yb complex but with a slightly smaller C-Eu-C angle (C-Eu-C ) 136°, C-Yb-C ) 137°) and longer Eu-C bonds (Eu-C ) 261 pm, Yb-C ) 249/250 pm). Salt metathesis was then again applied successfully to synthesize the first divalent Sm alkyl, Sm[C(SiMe 3 ) 2 (SiMe 2 OMe)] 2 (THF) Frank T. Edelmann was born in Hamburg, Germany, in 1954. He studied chemistry from 1974 to 1979 at the University of Hamburg, where he obtained his Diplom in 1979 and doctoral degree in 1983. His Ph.D. thesis entitled "The chemistry of the tricarbonyl(fulvene) chromium complexes" was carried out under the supervision of Prof. Ulrich Behrens. This was followed by two years (1983−1985) of postdoctoral research as a Feodor Lynen Fellow of the Alexander-von-Humboldt Foundation in the groups of Professors Josef Takats (

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Section: Trivalent Lanthanide Derivativesmentioning

confidence: 79%

Synthesis and Structural Chemistry of Non-Cyclopentadienyl Organolanthanide Complexes

2002

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“…Bei einem dieser Ansätze erhielten wir auch Einkristalle von [KNPCy 3 ] 4 ·2OPCy 3 (2), die wir wie 1 ebenfalls Kristallographisch charakterisiert haben. Als Ursache für die Anwesenheit von OPCy 3 im Reaktionsansatz vermuten wir unbeabsichtigtes Eintragen von Wasser bei der Herstellung des Eduktes Cy 3 …”

Section: Ergebnisseunclassified

“…Das zusätzlich in das Gitter eingelagerte DME-Molekül hat keine Solvateigenschaften. Als Folge von Fehlordnung des an Li(1) gebundenen DME-Moleküls erreicht das [Li 4 [3]. Sie entsprechen aber recht gut den zwischen den beiden Li 3 N 3 -Sechsringen bestehenden Bindungslängen von im Mittel 203,1 pm [3].…”

Section: [Li 4 (Npph 3 )(Osime 2 Npph 3 ) 3 (Dme)] ·unclassified

“…Als Folge von Fehlordnung des an Li(1) gebundenen DME-Moleküls erreicht das [Li 4 [3]. Sie entsprechen aber recht gut den zwischen den beiden Li 3 N 3 -Sechsringen bestehenden Bindungslängen von im Mittel 203,1 pm [3]. Etwas kürzer sind die Li-N-Bindungen auch in [LiBr·LiNPPh 3 (THF) 2 ] 2 [15] mit "heteroleptischem" Li 4 Br 2 N 2 -Heterokuban-Gerüst mit einem Mittelwert von 199,3 pm.…”

Section: [Li 4 (Npph 3 )(Osime 2 Npph 3 ) 3 (Dme)] ·unclassified

“…Tabelle 1 Kristalldaten und Angaben zu den Kristallstrukturbestimmungen von [KNP(cyclo-C 6 H 11 ) 3 ] 4(1), [KNP(cyclo-C 6 H 11 ) 3 ] 4 · 2OP(cyclo-C 6 H 11 ) 3 ] (2), [CsNP(cyclo-C 6 H 11 ) 3 ] 4 ·4OP(cyclo-C 6 H 11 )3 (3) und [[Li 4 (NPPh 3 )(OSiMe 2 NPPh 3 ) 3 (DME)]·1/2DME(4) …”

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Phosphaniminate von Alkalimetallen: Die Kristallstrukturen von [KNPCy3]4, [KNPCy3]4·2OPCy3, [CsNPCy3]4·4OPCy3 und [Li4(NPPh3)(OSiMe2NPPh3)3(DME)]

Gröb

Chitsaz

Harms

et al. 2002

Z. anorg. allg. Chem.

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The alkalimetal phosphoraneiminates [KNPCy3]4, (1) [KNPCy3]4·2OPCy3 (2) and [CsNPCy3]4·4OPCy3 (3) (Cy = cyclohexyl) which are obtainable by the reaction of pottassium amide or cesium amide with Cy3PI2 or Cy3PBr2 in liquid ammonia, as well as the lithium derivative [Li4(NPPh3)(OSiMe2NPPh3)3(DME)] (4) have been characterized by crystal structure determinations. 4 has been formed by the insertion reaction of silicon greaze (‐OSiMe2)n into the LiN bonds of [LiNPPh3]6 in DME solution (DME = 1, 2‐dimethoxyethane). 1: Space group P&1macr;, Z = 2, lattice dimensions at 193 K: a = 1389.8(1); b = 1408.1(1); c = 2205.2(2) pm; α = 78.952(10)?; β = 81.215(10)?; γ = 66.232(8)?; R1 = 0.0418. 2: Space group Pbcn, Z = 4, lattice constants at 193 K: a = 2943.6(2); b = 2048.2(1); c = 1893.8(1) pm; R1 = 0.0428. 3: Space group Cmc21, Z = 4, lattice dimensions at 193 K: a = 2881.6(2); b = 2990.2(2); c = 1883.7(2) pm; R1 = 0.0586. 4·1/2DME: Space group R&3macr;c, Z = 12, lattice dimensions at 193 K: a = b = 1583.5(1); c = 11755.3(5) pm; R1 = 0.0495. All complexes have heterocubane structures. In 1‐3 they are formed by four alkali metal atoms and by the nitrogen atoms of the (μ3‐NPCy3‐) groups, whereas 4 forms a "heteroleptic" Li4NO3 heterocubane.

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[MoN(NPPh3)3] - ein monomerer Nitrido-Komplex des Molybdäns

Dietrich

Neumüller

Dehnicke

1998

Z. anorg. allg. Chem.

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Reaktionen von LiNPPh3 mit den Cyclooctatetraenid-Komplexen [Ln(C8H8)Cl(THF)2]2 von Cer und Samarium. Die Kristallstrukturen von [LiNPPh3]6, [Ln(C8H8)Li3Cl2(NPPh3)2(THF)3] (Ln = Ce, Sm) und [Li(THF)4][Sm(C8H8)2]

Cited by 33 publications

References 3 publications

Synthesis and Structural Chemistry of Non-Cyclopentadienyl Organolanthanide Complexes

Synthesis and Structural Chemistry of Non-Cyclopentadienyl Organolanthanide Complexes

Phosphaniminate von Alkalimetallen: Die Kristallstrukturen von [KNPCy3]4, [KNPCy3]4·2OPCy3, [CsNPCy3]4·4OPCy3 und [Li4(NPPh3)(OSiMe2NPPh3)3(DME)]

[MoN(NPPh3)3] - ein monomerer Nitrido-Komplex des Molybdäns

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