Phosphide Delivery to a Cyclotrisilene

Robinson, Thomas; Cowley, Michael J.; Scheschkewitz, David; Goicoechea, José M.

doi:10.1002/anie.201409908

Cited by 79 publications

(44 citation statements)

References 54 publications

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“…[48,49] Theu se of phosphaethynolate as source of P À has also been observed in the reaction between an unsaturated three-membered silicon ring (a cyclotrisilene) and Na(OCP) (Scheme 7). [50] This highly solvent dependent reaction gives bright yellow crystals of ab icyclic compound in moderate yield in which the P=C bond of the OCP À anion has been thermally broken. Subsequent photolysis leads to the blue-green fourmembered Si 3 Ph eterocycle.N ote that during the photolysis not only CO is extruded but also formally atriisopropylphenyl (Tipp) group migrated from the Si atom trans to phosphorus to a cis-position.…”

Section: Angewandte Chemiementioning

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: Angewandte Chemiementioning

confidence: 99%

The Chemistry of the 2‐Phosphaethynolate Anion

2018

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“…It is noteworthy that the B À PCO skeleton is converted to B À OCP after CAAC-promoted rearrangement. The C1 À P1 bond [1.7369(15) ] possesses double bond character and is shorter than the C23ÀP1 single bond [1.8354 (14) ].…”

Section: Angewandte Chemiementioning

confidence: 99%

“…Na(OCP)·(dioxane) x chemistry has been explored comprehensively, [9] and compounds with terminal PCO anions have been used as monoatomic phosphide transfer reagents through decarbonylation. [14] The bright yellow solution of 2 turned dark red after irradiation with UV light for 6 hours (Scheme 2). A new singlet resonance appeared at 142.7 ppm in the 31 P{ 1 H} NMR spectrum of the reaction mixture and a broad resonance at 51.1 ppm was observed in the 11 B{ 1 H} NMR spectrum.…”

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Crystalline BP‐Doped Phenanthryne via Photolysis of The Elusive Boraphosphaketene

et al. 2020

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The synthesis and reactivity study of the first isolable boraphosphaketene, cyclic(alkyl)(amino) carbene (CAAC)‐borafluorene‐P=C=O (2), is described. Photolysis of compound 2 results in the formation of CAAC‐stabilized BP‐doped phenanthryne (3) through tandem decarbonylation, monoatomic phosphide insertion, and ring‐expansion. Notably, while BN‐doped phenanthryne was previously discussed as a reactive intermediate which could not be isolated, the heavier BP‐doped analogue exhibits remarkable solution and solid‐state stability. The reactivity of 2 with stable carbenes was also explored. Addition of CAAC to 2 led to migration of the original CAAC ligand from boron to phosphorus and coordination of the added CAAC to carbon, affording compound 4. Reaction of 1,3‐diisopropyl‐4,5‐dimethylimidazol‐2‐ylidene (NHC) with 2 resulted in N−C bond activation to give the unusual spiro‐heterocyclic compound (5).

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“…Demgegenüber stehen nur wenige bekannte cyclische Verbindungen mit einer oder mehreren Si=P‐Doppelbindungen. Die Beispiele beinhalten die schweren Cyclobutadiene I und II , das schwere Cyclobuten‐Kongener III sowie schwere Heteroanaloga des Cyclopentadienyl‐Kations IV und Benzol V (Abbildung ). Dreigliedrige, cyclische Phosphasilene sind bemerkenswerterweise nicht literaturbekannt; sogar Berichte über gesättigte, dreigliedrige Ringe bestehend aus Silicium und Phosphor (Si 2 P und SiP 2 ) sowie Phosphasilirene mit einer endocyclischen P=C‐Doppelbindung sind selten.…”

Section: Figureunclassified

Ein dreigliedriges cyclisches Phosphasilen

Heider¹,

Willmes²,

Mühlhausen³

et al. 2019

Angewandte Chemie

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Kleine ungesättigte Phosphorcyclen sind aufgrund ihrer Ringspannung und der zusätzlichen Funktionalitäten der Doppelbindung und des freien Phosphor‐Elektronenpaars vielseitige Reagenzien. Wir berichten hier über die Synthese und Isolierung des kleinstmöglichen, cyclischen Phosphasilens als stabiles Addukt mit einem N‐heterocyclischen Carben (NHC). Erste Reaktivitätsstudien zeigen, (a) dass der PSi2‐Ring mittels des freien Elektronenpaares am Phosphor ein kompetenter Ligand für das Fe(CO)4 Fragment ist und (b) dass die Abstraktion des NHCs mit BPh3 zu einer raschen Kopf‐Kopf‐ oder Kopf‐Schwanz‐Dimerisierung der PSi2‐Einheit führt. Die relativ leichte NHC‐Abspaltung deutet die Verfügbarkeit der P=Si‐Doppelbindung für weitere Manipulationen an.

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Phosphide Delivery to a Cyclotrisilene

Cited by 79 publications

References 54 publications

The Chemistry of the 2‐Phosphaethynolate Anion

The Chemistry of the 2‐Phosphaethynolate Anion

Crystalline BP‐Doped Phenanthryne via Photolysis of The Elusive Boraphosphaketene

Ein dreigliedriges cyclisches Phosphasilen

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