Synthesis and Characterization of Primary and Secondary Allenyl- and Alkynylarsines

Lassalle, L.; Legoupy, Stéphanie; Guillemin, Jean‐Claude

doi:10.1021/ic00126a047

Cited by 23 publications

(23 citation statements)

References 3 publications

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“…All chemicals were used without further purification. Tributylstannane, allenyltributylstannane, vinyltributylstannane, allenylphosphine ( 1 ), allenylarsine ( 3 ), and divinylarsine ( 4 ) were prepared as previously reported.…”

Section: Methodsmentioning

confidence: 99%

“…The presence of arsaalkenes in the products formed by vaporization of primary vinylarsines on a solid base has been evidenced by analysis of the gaseous flow by photoelectron spectroscopy , ) Consequently, we thought that the base-induced rearrangement of the allenyl and divinyl derivatives could lead, via a similar rearrangement, to the corresponding 1- and 2-hetero dienes containing a phosphorus, arsenic, or antimony atom. We report here a study devoted to the base-induced rearrangement of the two phosphorus and two arsenic parent compounds (allenylphosphine ( 1 ), divinylphosphine ( 2 ), allenylarsine ( 3 ), and divinylarsine ( 4 )), potential precursors of the corresponding 1- and 2-hetero dienes.…”

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confidence: 99%

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Allenyl and Divinyl Phosphines, Arsines, and Stibines as Potential Precursors of the Corresponding 1- and 2-Phospha, 1- and 2-Arsa, and 1- and 2-Stiba Dienes

1996

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The base-induced rearrangement of divinylphosphine led to the corresponding 3-phospha-1,3-pentadiene, which is sufficiently stable to be detected at room temperature by 31P NMR spectroscopy. This diene was trapped by addition of 2-propanethiol to the reaction mixture. Under similar conditions, the transient 1-phospha-1,3-butadiene and 3-arsa-1,3-pentadiene were chemically trapped. Divinylstibine and allenylstibine, both new compounds and potential precursors of stibadienes, were also prepared.

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Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

Allenyl and Divinyl Phosphines, Arsines, and Stibines as Potential Precursors of the Corresponding 1- and 2-Phospha, 1- and 2-Arsa, and 1- and 2-Stiba Dienes

1996

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“…Das dabei gebildete, thermisch unbesta È ndige Ethinylarsan lagert bei 80°C in Anwesenheit von Dinatriumcarbonat unter 1,3-Verschiebung beider Wasserstoffatome vom Arsen-zum Kohlenstoffatom u È ber ein nur postuliertes 1-Arsaallen in das gesuchte k 3 -Arsaalkin um. Auch Propylidinarsan ist auf diesem Weg zuga È nglich [17].…”

Section: Li] + [S±c≡p] ± a Bunclassified

[(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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“…The apparatus already described for the reduction of α,β‐unsaturated chloroarsines was used 32. A two‐necked flask equipped with a stirring bar and a septum and containing mercury chloride 1 a – e (3 mmol), a small amount of a radical inhibitor (duroquinone, ≈20 mg), and chlorotributylstannane (15 mL) as the solvent was fitted on a vacuum line (0.01 kPa), cooled at about 0 °C by immersion in an ice bath, and degassed.…”

Section: Methodsmentioning

confidence: 99%

On the Structures, Lifetimes, and Infrared Spectra of Alkylmercury Hydrides

et al. 2014

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A series of six small alkylmercury hydrides of the general formula RHgH with R=methyl, ethyl, n-propyl, isopropyl, n-butyl, and 3-butenyl were obtained by reduction in vacuo of the corresponding mercury halide with tributyltin hydride in the presence of a radical inhibitor. These very reactive compounds, which have to be removed from the reaction mixture as they are formed, were characterized by (1)H NMR and (13)C NMR spectroscopy. The IR spectra of n-propyl-, isopropyl-, n-butyl-, and 3-butenylmercury hydride were recorded for the first time. All compounds were then studied by density functional theory calculations on the basis of a recent theoretical assessment for alkylmercury compounds performed by our group. Comparison of the experimental and theoretical results allowed the assignment of the vibrational modes in an unambiguous way, in spite of the low intrinsic stability of some of the derivatives investigated. The experimental procedure implemented for registering the IR spectra of these unstable species in the gas phase allowed us to obtain reasonable estimates of their lifetimes.

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Synthesis and Characterization of Primary and Secondary Allenyl- and Alkynylarsines

Cited by 23 publications

References 3 publications

Allenyl and Divinyl Phosphines, Arsines, and Stibines as Potential Precursors of the Corresponding 1- and 2-Phospha, 1- and 2-Arsa, and 1- and 2-Stiba Dienes

Allenyl and Divinyl Phosphines, Arsines, and Stibines as Potential Precursors of the Corresponding 1- and 2-Phospha, 1- and 2-Arsa, and 1- and 2-Stiba Dienes

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

On the Structures, Lifetimes, and Infrared Spectra of Alkylmercury Hydrides

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