Alkylidinphosphane und ‐arsane. I [P ≡ CS]−[Li(dme)3]+ – Synthese und Struktur

Becker, Gerd; Hübler, Klaus

doi:10.1002/zaac.19946200303

Cited by 71 publications

(58 citation statements)

References 58 publications

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“…[67] To rationalise this reactivity,afourmembered cyclic intermediate was proposed, the formation of which involves cyclization of the PCand C=Sbonds of the reactants,f ollowed by a[ 2 + +2] cycloreversion. [67] To rationalise this reactivity,afourmembered cyclic intermediate was proposed, the formation of which involves cyclization of the PCand C=Sbonds of the reactants,f ollowed by a[ 2 + +2] cycloreversion.…”

Section: Four-membered Heterocyclesmentioning

confidence: 99%

The Chemistry of the 2‐Phosphaethynolate Anion

2018

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In all likelihood the first synthesis of the phosphaethynolate anion, PCO , was performed in 1894 when NaPH was reacted with CO in an attempt to make Na(CP) accompanied by elimination of water. This reaction was repeated 117 years later when it was discovered that Na(OCP) and H are the products of this remarkable transformation. Li(OCP) was synthesized and fully characterized in 1992 but this salt proved to be too unstable to allow for a detailed investigation of its chemistry. It was not until the heavier analogues of this lithium salt were isolated, Na(OCP) and K(OCP) (both of which are remarkably stable and can be even dissolved in water), that the chemistry of this new functional group could be explored. Here we review the chemistry of the 2-phosphaethynolate anion, a heavier phosphorus-containing analogue of the cyanate anion, and describe the wide breadth of chemical transformations for which it has been thus far employed. Its use as a ligand, in decarbonylative and deoxygenative processes, and as a building block for novel heterocycles is described. In the mere twenty-six years since Becker first reported the isolation of this remarkable anion, it has become a fascinating reagent for the synthesis of a vast library of, often unprecedented, molecules and compounds.

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Section: Four-membered Heterocyclesmentioning

confidence: 99%

The Chemistry of the 2‐Phosphaethynolate Anion

2018

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“…In vorausgehenden Vero È ffentlichungen berichteten wir u È ber die unerwartete Synthese der Verbindungen Bis(1,2-dimethoxyethan-O,O')lithoxymethylidinphosphan (A) [2,3] und Tris(1,2-dimethoxyethan-O,O')lithium-phosphaethinylsulfanid (B) [3,4] sowie nachfolgende, bislang aber nicht abgeschlossene Untersuchungen zur Reaktivita È t { [1,5]; s. auch [6]}. Da diese k 3 -Phosphaalkine in Lo È sung u È berraschend stabil und einfach zuga È nglich sind, lagen Versuche zur Synthese der entsprechenden Arsane nahe.…”

Section: Introductionunclassified

[(dme)Li]3As7 – Synthese und Aufbau einer Verbindung mit Nortricyclen-Struktur

Hübler

Becker

1998

Z. anorg. allg. Chem.

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Während sich Bis(tetrahydrofuran)lithium‐bis(trimethylsilyl)phosphanid mit Dimethylcarbonat in 1,2‐Dimethoxyethan unter Eliminierung von Methoxytrimethylsilan zum λ3‐Phosphaalkin (dme)2Li–O–C≡P umsetzt [2], führt die entsprechende Reaktion des homologen Arsanids unter zusätzlicher Bildung von Kohlenmonoxid zum Neutralkomplex [(dme)Li]3As7 (1 a). Beim Abkühlen einer gesättigten Lösung in 1,2‐Dimethoxyethan und wenig Diethylether erhält man die Verbindung mit 40proz. Ausbeute als Kokristallisat 1 a · OEt2; die in Form bernsteinfarbener Stäbchen isolierten Kristalle erweisen sich jedoch unter Vortäuschung hexagonaler Symmetrie als partiell meroedrisch verdrillingt. Die erst nach eingehender Analyse des Datensatzes in der monoklinen Raumgruppe P21/n mögliche Strukturbestimmung {a1 = 1123,0(2); b = 1485,5(3); c1 = 1945,1(4) pm; β = 90,00(3)° bei –100 ± 3 °C; Z = 4 Formeleinheiten; wR2 = 0,280} ergibt eine hexagonal dichteste Packung der Neutralkomplexe mit noch leicht beweglichen Diethylether‐Molekülen in den für eine derartige Struktur typischen Kanälen. Je zwei einfach negativ geladene Arsenatome des Heptarsanortricyclen‐Gerüstes koordinieren an jeweils eines der insgesamt drei [(dme)Li]+‐Kationen; die mittleren Bindungslängen und ‐winkel im As73–‐Polyeder (Asa–Ase 240,7; Ase–Asb 235,3; Asb–Asb 249,8 pm; Ase–Asa–Ase 101,0°; Asa–Ase–Asb 99,6°; Ase–Asb–Asb 105,1°; Asb–Asb–Asb 60,0°) entsprechen Werten aus analogen Verbindungen. Über ab initio‐Berechnungen und anschließende NBO‐Analysen an den Spezies As73– (2) und As7H3 (3) lassen sich auffällige Änderungen in den charakteristischen Parametern von anionischem und molekularem Heptarsanortricyclen‐Gerüst erklären.

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“…Thes tructure of the PCS À anion was previously reported by Becker and Hübler as the [Li(DME) 3 ][PCS] salt (P À C: 1.555(11) ;C ÀS: 1.620 (11) ;P -C-S:1 78.9(7)8 8), [14] and our data for [Na (18-crown-6)(THF) 2 ][PCS] compare well with reported values (PÀC: 1.579(4) ;C ÀS: 1.613(4) ;P -C-S: 179.3(3)8 8). ThePÀCbond length is identical to that previously determined for the PCO À ion in [K (18-crown-6)][PCO], 1.579(3), which approximates the value predicted for aP C triple bond (1.54 ).…”

mentioning

confidence: 98%

“…Ther eport of several novel syntheses of the ion as the more stable sodium and potassium salts has rekindled interest in this reagent. [13] To date,c yanate analogues containing both heavier Group 15 and Group 16 elements are limited to the 2phosphaethynthiolate anion (PCS À )which can be synthesised by reaction of PCO À with CS 2 .Aswith PCO À ,this species was first isolated by Becker and Hübler, [14] and its chemistry has largely been limited to fundamental coordination chemistry studies and some gas-phase measurements. [9][10][11] Theh eavier arsenic-containing ion, AsCO À ,w as first isolated in 2016 by our research group, [12] and promises to be as imilarly versatile reagent in chemical synthesis,h aving already been employed for the synthesis of several novel molecules.…”

mentioning

confidence: 99%

“…[9][10][11] Theh eavier arsenic-containing ion, AsCO À ,w as first isolated in 2016 by our research group, [12] and promises to be as imilarly versatile reagent in chemical synthesis,h aving already been employed for the synthesis of several novel molecules. [13] To date,c yanate analogues containing both heavier Group 15 and Group 16 elements are limited to the 2phosphaethynthiolate anion (PCS À )which can be synthesised by reaction of PCO À with CS 2 .Aswith PCO À ,this species was first isolated by Becker and Hübler, [14] and its chemistry has largely been limited to fundamental coordination chemistry studies and some gas-phase measurements. [15,16] Clearly,there are still anumber of valence isoelectronic ions related to such species that have yet to be experimentally realised.…”

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confidence: 99%

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A General Synthesis of Phosphorus‐ and Arsenic‐Containing Analogues of the Thio‐ and Seleno‐cyanate Anions

et al. 2018

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Ag eneral synthetic protocol for the synthesis of phosphorus-and arsenic-containing analogues of the thio-and seleno-cyanate anions is reported. This procedure allows for the isolation of three unprecedented species:t he phosphaethynselenolate,P CSe À (1), the arsaethynthiolate,A sCS À (2), and the arsaethynselenolate,A sCSe À (3), anions.T he structures,e lectronic properties,a nd spectroscopic signatures of these species are reported. Scheme 1. Synthesis of [Na(18-crown-6)(THF) 2 ][PnCCh]( where Pn = P, As; Ch = S, Se).Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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Alkylidinphosphane und ‐arsane. I [P ≡ CS]⁻[Li(dme)₃]⁺ – Synthese und Struktur

Cited by 71 publications

References 58 publications

The Chemistry of the 2‐Phosphaethynolate Anion

The Chemistry of the 2‐Phosphaethynolate Anion

[(dme)Li]3As7 – Synthese und Aufbau einer Verbindung mit Nortricyclen-Struktur

A General Synthesis of Phosphorus‐ and Arsenic‐Containing Analogues of the Thio‐ and Seleno‐cyanate Anions

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