NHC-Mediated Aggregation of P<sub>4</sub>:  Isolation of a P<sub>12</sub> Cluster

Masuda, Jason D.; Schoeller, Wolfgang W.; Donnadieu, Bruno; Bertrand, Guy

doi:10.1021/ja077296u

Cited by 260 publications

(165 citation statements)

References 26 publications

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“…Die Aktivierung der beiden prominentesten 20-Valenzelektronen-Käfige P 4 und As 4 mittels Übergangsmetallkom-plexen oder Carbenen wurde in den vergangenen vier Jahrzehnten ausgiebig untersucht, was zur Entstehung einer großen Vielfalt faszinierender Produkte führte. In Abhän-gigkeit von den Reaktionsbedingungen und Reaktanten fungierten die Käfige als E 4 -Liganden oder unterlagen komplexen Bindungsspaltungs-und Fragmentierungsreaktionen.…”

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Bildung eines homoatomaren, polycyclischen Bismut‐Polyanions, [Bi₁₁]³⁻, durch Pyridin‐unterstützte Zersetzung von [GaBi₃]²⁻

et al. 2014

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+ -Salzen der Anionen in Ethan-1,2-diamin (en) realisiert, wohingegen das Verhalten der Vorstufen in anderen chemischen Umgebungen nur unzureichend untersucht ist.[10] Wir planten daher, unsere bisherigen Reaktionen in andere Lçsungsmittel zu übertragen, und begannen mit der Untersuchung der Lçslichkeit und des Reaktionsverhaltens von [K([2.2.2]crypt)] 2 (GaBi 3 )·en [7] in Pyridin (py). Im Gegensatz zu allen anderen Studien kristallisierte nach Abfiltrieren eines grauschwarzen Rückstands (nach 3 h Rühren) und Überschichtung der Lçsung mit Toluol allerdings nicht die Ausgangsverbindung. Stattdessen entstanden innerhalb von drei Tagen schwarze, für die Einkristallstrukturanalyse [11] geeignete Nadeln der Verbindung

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Bildung eines homoatomaren, polycyclischen Bismut‐Polyanions, [Bi₁₁]³⁻, durch Pyridin‐unterstützte Zersetzung von [GaBi₃]²⁻

et al. 2014

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“…[17][18][19] In order to study the feasibility of such a hypothesis we turned to calculations to investigate the possible conformations of the proposed Ph 3 SnP 3 intermediate. Both (η 1 -P 3 )SnPh 3 and (η 3 -P 3 )SnPh 3 structures were considered.…”

mentioning

confidence: 99%

Shuttling P₃ from Niobium to Rhodium: The Synthesis and Use of Ph₃SnP₃(C₆H₈) as a P₃⁻ Synthon

Cossairt

Cummins

2010

Angew Chem Int Ed

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Seeking new methods for phosphorus incorporation directly from its molecular elemental form, P 4 , we have begun to focus on cyclo-P 3 complexes as a versatile class of intermediates. [1][2][3][4] While it is well documented that a common result of P 4 activation by transition-metal complexes is replacement of a single vertex of the P 4 tetrahedron by an ML n fragment, such cyclo-P 3 complexes were not recognized until recently for their potential as phosphorus transfer agents. 2-6 Accordingly, anionic cyclo-P 3 complexes of niobium have been shown to serve as sources of P 3 3− upon stoichiometric treatment with suitable tripositive electrophiles, including acid chlorides leading to triphosphabutadiene intermediates, 2,3 or AsCl 3 leading to AsP 3 . 4,7 With the present work we illustrate a new approach to phosphorus transfer chemistry by way of a P 3 1− synthon, the Ph 3 SnP 3 (C 6 H 8 ) molecule, that is both nucleophilic at phosphorus and capable of losing neutral 1,3-cyclohexadiene upon treatment with an appropriate P 3 1− acceptor. The Ph 3 SnP 3 (C 6 H 8 ) molecule is itself obtained in an efficient three-step sequence involving P 4 activation, functionalization with triphenyltin chloride, and pyridine-N-oxide-elicited triphosphirene elimination in the presence of 1,3-cyclohexadiene (Scheme 1).Facile access to [Na][(η 3 -P 3 )Nb(ODipp) 3 ] (Dipp = 2,6-i Pr 2 C 6 H 3 ), a convenient source of P 3 3− , is gained through reduction of the complex Cl 2 Nb(ODipp) 3 in the presence of white phosphorus. 4,8,9 The anionic nature of this cyclo-P 3 niobium complex imparts demonstrable nucleophilic character at the P 3 ring, allowing for reaction with a range of mild electrophiles. 1,4 Treatment of [Na][(η 3 -P 3 )Nb(ODipp) 3 ] with Ph 3 SnCl results in loss of NaCl and formation of (η 2 -Ph 3 SnP 3 )Nb(ODipp) 3 (1, Scheme 1). The phosphorus NMR spectrum of 1 consists of a single sharp singlet at −235 ppm with 117/119 Sn satellites 1 J119 Sn−P = 336 Hz, 1 J117 Sn−P = 321 Hz) (Figure 1a). This sharp singlet is indicative of whizzing of the Ph 3 Sn moiety about the cyclo-P 3 ring. 1,10-12 Variable temperature NMR spectra obtained as low as −90 • C reveal no locking out of this movement on the NMR time scale.The niobium-phosphorus interaction in 1 may be regarded as side-on coordination of a diphosphene (RP=PR) to a strongly π-donating d 2 Nb(ODipp) 3 fragment. 13 To liberate the triphosphirene molecule P 3 SnPh 3 from niobium, complex 1 was treated with a stoichiometric amount of pyridine-N-oxide in the presence of excess 1,3-cyclohexadiene, 14,15 the latter to serve as a trapping agent; this protocol results in formation of the desired Diels-Alder adduct Ph 3 SnP 3 (C 6 H 8 ), 2, together with 0.5 equiv of the known niobium oxo dimer [ONb(ODipp) 3 ] 2 (Scheme 1). 16 Compound 2 was isolated in 65% yield by filtration as it selectively precipitated upon concentration of the ethereal reaction mixture. Conveniently, compound 2 could also be prepared directly in a single pot, without isolation of complex 1, in an overall yi...

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“…The lowest energy barrier is predicted for 5, a hitherto experimentally unknown silylene. As has been shown in carbene chemistry [14], such species may become more stable by steric protection with bulky substituents. The largest energy barrier results for 3 (and to a lesser extent for 4), which also shows large S-T energy separations (Table 1).…”

Section: Reaction Barriersmentioning

confidence: 75%

“…Experimental studies in the 1980s [7][8][9] reveal that the degradation process is strongly dependent on a diverse set of conditions: the choice of the nucleophile, the ratio of the nucleophile with respect to P 4 , etc. A more clear-cut understanding of these reactions comes from the systematic investigation into metal fragments involved in white phosphorus degradation [10][11][12], as well as, more recently, by reactions with carbenes [13,14] and, in one report, on silylene addition to white phosphorus [15]. Detailed experimental reaction studies are also known for phosphenium cations [16,17].…”

Section: Introductionmentioning

confidence: 99%

Dispersion-corrected energy barriers for silylene addition to white phosphorus, a density functional investigation into substituent effects

Schoeller

2010

Theor Chem Acc

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A density functional investigation into differently substituted silylenes with respect to the first step in the addition to white phosphorus is presented. The investigations include dispersion corrections in the density functional treatment. They become sizable for the transition state geometries for the silylenes as they become increasingly substituted by bulky groups. Hence, dispersion corrections are essential for a quantum chemical treatment of real molecules using density functional theory. The different singlet-triplet energy separations of differently substituted silylenes were also investigated and compared with calculated activation barriers for the first step in the addition reaction.

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NHC-Mediated Aggregation of P₄: Isolation of a P₁₂ Cluster

Cited by 260 publications

References 26 publications

Bildung eines homoatomaren, polycyclischen Bismut‐Polyanions, [Bi₁₁]³⁻, durch Pyridin‐unterstützte Zersetzung von [GaBi₃]²⁻

Bildung eines homoatomaren, polycyclischen Bismut‐Polyanions, [Bi₁₁]³⁻, durch Pyridin‐unterstützte Zersetzung von [GaBi₃]²⁻

Shuttling P₃ from Niobium to Rhodium: The Synthesis and Use of Ph₃SnP₃(C₆H₈) as a P₃⁻ Synthon

Dispersion-corrected energy barriers for silylene addition to white phosphorus, a density functional investigation into substituent effects

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NHC-Mediated Aggregation of P4: Isolation of a P12 Cluster

Cited by 260 publications

References 26 publications

Bildung eines homoatomaren, polycyclischen Bismut‐Polyanions, [Bi11]3−, durch Pyridin‐unterstützte Zersetzung von [GaBi3]2−

Bildung eines homoatomaren, polycyclischen Bismut‐Polyanions, [Bi11]3−, durch Pyridin‐unterstützte Zersetzung von [GaBi3]2−

Shuttling P3 from Niobium to Rhodium: The Synthesis and Use of Ph3SnP3(C6H8) as a P3− Synthon

Dispersion-corrected energy barriers for silylene addition to white phosphorus, a density functional investigation into substituent effects

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NHC-Mediated Aggregation of P₄: Isolation of a P₁₂ Cluster

Bildung eines homoatomaren, polycyclischen Bismut‐Polyanions, [Bi₁₁]³⁻, durch Pyridin‐unterstützte Zersetzung von [GaBi₃]²⁻

Bildung eines homoatomaren, polycyclischen Bismut‐Polyanions, [Bi₁₁]³⁻, durch Pyridin‐unterstützte Zersetzung von [GaBi₃]²⁻

Shuttling P₃ from Niobium to Rhodium: The Synthesis and Use of Ph₃SnP₃(C₆H₈) as a P₃⁻ Synthon