Synthese, Charakterisierung und Kristallstrukturen der Pseudohalogen-Kronenether-Komplexe [K([18]krone-6)(X)(OPPh3)] (X = N3–, OCN– und SCN–)

Keßenich, Elmar; Polborn, Kurt; Schulz, Axel

doi:10.1002/1521-3749(200111)627:11<2506::aid-zaac2506>3.0.co;2-s

Cited by 11 publications

(3 citation statements)

References 3 publications

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“…The remaining orange oil was recrystallized from anhydrous hexane over a period of 14 days. We assume that oxygen was introduced by either THF or during the recrystallization procedure . When we attempted to isolate a sample for elemental analysis, the crystals released solvent molecules, hence the reported data are fairly inaccurate.…”

Section: Methodsmentioning

confidence: 99%

Mono-, Di-, and Tricoordinated Phosphorus Attached to a N−N Unit: An Experimental and Theoretical Study

et al. 2005

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N,N',N'-[Tris(trimethylsilyl)]hydrazino-diphenylphosphane, (TMS)2 N-(TMS)N-PPh2 (1), and N,N',N'-[tris(trimethylsilyl)]hydrazino-phenyl(chloro)phosphane, (TMS)2 N-(TMS)N-P(Cl)Ph2 (2), were obtained in the reaction of bis-[lithium-tris(trimethylsilyl)hydrazide] with Ph(n)PCl(3 - n) (n = 1, 2). The structure and bonding of both species are discussed on the basis of experimentally observed (X-ray, Raman, NMR, and MS) and theoretically obtained data (B3LYP/6-31G(d,p), NBO analysis). Oxidation with sulfur and selenium results in the formation of (TMS)2 N-(TMS)N-P(S)Ph2 (4), (TMS)2 N-(TMS)N-P(Se)Ph2 (5), (TMS)2 N-(TMS)N-P(S)Ph(Cl) (6), and (TMS)2 N-(TMS)N-P(Se)Ph(Cl) (7). Moreover, the thermal decomposition of N,N',N'-[tris(trimethylsilyl)]hydrazine-dichlorophosphane, (TMS)2 N-(TMS)N-PCl2 (3) and the reaction with magnesium have been investigated. The formation and molecular structure of the novel MgCl2(THF)2 x 2Mg[(TMS)NP(O)2 N(TMS)2](THF) (8) salt containing the hitherto unknown (TMS)NP(O)2 N(TMS)2(2-) anion are discussed. DFT calculations (B3LYP/6-311+G(3df,2p)//B3LYP/6-31G(d,p)) are used to evaluate the bonding, ground-state structures, and energy landscape for the different isomers of 3: the thermodynamics and kinetics of the successive elimination of chlorotrimethylsilane (TMS-Cl) resulting in the formation of covalent azide analogues such as TMS-PNN or TMS-NNP.

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Section: Methodsmentioning

confidence: 99%

Mono-, Di-, and Tricoordinated Phosphorus Attached to a N−N Unit: An Experimental and Theoretical Study

et al. 2005

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“…1) hervorgeht, ist das zentrale Kalium-Ion achtfach koordiniert, wobei sich die Kalium-Sauerstoff-Abstände um bis zum 20fachen der Standardabweichung unterscheiden, aber die K-O-Abstände liegen im gleichen Bereich (2.7Ϫ2.8 Å ) wie die in anderen K(18-Krone-6)X Verbindungen (X ϭ z.B. NCS [10], NCS·SO 2 [11], N 3 ·OPPh 3 [12]). Die CϵN-Bindungslänge beträgt 1.154 (7) Der Kronenether ist mehrfach gefaltet, wobei die sechs Sauerstoffatome aus der "besten Ebene" weit herausstehen.…”

Section: Röntgenstrukturanalyse Von [(18-krone-6)kalium]isocyanacetatunclassified

Alkaliisocyanacetate. Synthese und Struktur von [K(18‐Krone‐6)](O₂CCH₂NC)

Fehlhammer

Schrölkamp

Hoyer

et al. 2005

Zeitschrift anorg allge chemie

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The alkali isocyanoacetates M ϩ [O 2 CCH 2 NC] Ϫ (M ϭ Li,-Na,K,Cs) (1a-d) are synthesized by reaction of ethyl isocyanoacetate with the respective alkali hydroxides in ethanol and characterized by IR, NMR ( 1 H, 13 C), and mass spectrometry (FAB). In alcoholic solution as well as in the gas phase ion pairs and higher aggregated species are observed. In contrast, [K(18-crown-6)][O 2 CCH 2 NC] (2) which is obtained from 1c and 18-crown-6, Einleitung Kaliumisocyanacetat, K ϩ [CNCH 2 CO 2 ] Ϫ , wurde erstmals von Hoppe und Schöllkopf [1] durch Verseifung von Isocyanessigsäureethylester mit KOH erhalten. Isocyanacetat ist eine interessante Ausgangssubstanz für neuartige Verbindungen. So wurde [CNCH 2 CO 2 ] Ϫ zur Synthese von Isocyanacetylchlorid und von isocyansubstituierten β-Lactamen [1], zur Herstellung von Isocyanpeptiden (durch Umsetzung mit Aminosäure-oder Peptidestern) [2Ϫ4], von C-koordinierten Tetrazolato-Komplexen (durch Umsetzung mit Metallaziden) [5] sowie als Ligand genutzt [6]. Die Verseifung des Esters gelingt auch am metallkoordinierten Isocyanessigester (z.B. von [(OC) 5 WCNCH 2 CO 2 Et] zu [(OC) 5 WCNCH 2 CO 2 ] Ϫ [6]). Ergebnisse und DiskussionKalium-isocyanacetat fällt nach Reaktion von Isocyanessigsäureethylester mit Kaliumhydroxid bei 0°C in Ethanol [1] in Form von perlmuttartig glänzenden Blättchen an (Gl. (1)). Auf gleiche Weise erhält man mit LiOH, NaOH und CsOH die entsprechenden Lithium-, Natrium-und Caesium-isocyanacetate 1a,b und 1d in Ausbeuten zwischen 55 und 85 %. 3025 turns out to be a 1:1 electrolyte in solution (acetone); in the solid, the isocyanoacetate anion binds to K ϩ via the two carboxylate oxygen atoms resulting in an O 8 -coordinated metal atom.

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“…The synthesis and structures of similar complexes with the general formula [K(An)(18-crown-6)(Ph 3 PO)] of the hostguest type [1] were described in [2] (An = I, Br, and SCN) and in [3] (An = OCN, SCN, and N 3 ). X-ray diffraction analysis was carried out for the complexes with An = I [2] and An = OCN, SCN, and N 3 [3]. The crystal structures of these four complexes are isomorphic and highly symmetric (space group R 3 m ).…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Crystal Structure of (18-Crown-6)(nitrato)(triphenylphosphine oxide)potassium

Chekhlov

2005

Russ J Coord Chem

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A new complex (18-crown-6)(nitrato)(triphenylphosphine oxide)potassium ( I ) is synthesized, and its crystal structure is studied by X-ray diffraction analysis (space group R 3 m , a = 14.336 Å , c = 13.776 Å , Z = 3). The structure is solved by the direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.034 for 1122 independent reflections (CAD4 automated diffractometer, λ Mo K α radiation). Structure I contains a complex host-guest molecule [K ( NO 3 )(18 -crown-6)( Ph 3 PO)] with crystallographic symmetry 3 m (three planes m contain three Ph rings of the Ph 3 PO ligand and all O atoms of the crown ligand). The coordination polyhedron of the K + cation is a distorted hexagonal bipyramid with all the six O atoms of the crown ligand in the base, the O atoms of the Ph 3 PO ligand, and one (or two) O atoms of a disordered ligand in the axial positions. NO 3 -

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Synthese, Charakterisierung und Kristallstrukturen der Pseudohalogen-Kronenether-Komplexe [K([18]krone-6)(X)(OPPh3)] (X = N3–, OCN– und SCN–)

Cited by 11 publications

References 3 publications

Mono-, Di-, and Tricoordinated Phosphorus Attached to a N−N Unit: An Experimental and Theoretical Study

Mono-, Di-, and Tricoordinated Phosphorus Attached to a N−N Unit: An Experimental and Theoretical Study

Alkaliisocyanacetate. Synthese und Struktur von [K(18‐Krone‐6)](O₂CCH₂NC)

Synthesis and Crystal Structure of (18-Crown-6)(nitrato)(triphenylphosphine oxide)potassium

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Synthese, Charakterisierung und Kristallstrukturen der Pseudohalogen-Kronenether-Komplexe [K([18]krone-6)(X)(OPPh3)] (X = N3–, OCN– und SCN–)

Cited by 11 publications

References 3 publications

Mono-, Di-, and Tricoordinated Phosphorus Attached to a N−N Unit: An Experimental and Theoretical Study

Mono-, Di-, and Tricoordinated Phosphorus Attached to a N−N Unit: An Experimental and Theoretical Study

Alkaliisocyanacetate. Synthese und Struktur von [K(18‐Krone‐6)](O2CCH2NC)

Synthesis and Crystal Structure of (18-Crown-6)(nitrato)(triphenylphosphine oxide)potassium

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Alkaliisocyanacetate. Synthese und Struktur von [K(18‐Krone‐6)](O₂CCH₂NC)