The Reaction of Dipotassium Cyclooctatetraenide with Dichlorophenylphosphine. Rearrangements of 9-Phenyl-9-phosphabicyclo[6.1.0]nonatriene and 9-Phenyl-9-phosphabicyclo[4.2.1]nonatriene

Katz, Thomas J.; Nicholson, Christina R.; Reilly, C. A.

doi:10.1021/ja00968a029

Cited by 73 publications

(14 citation statements)

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“…In contrast, PCl 3 and PhPCl 2 produced neither ClP A nor PhP A upon treatment with Mg A ·3THF, instead giving unidentified phosphorus-containing products or cyclic oligophosphanes (PhP) n , respectively . In these two cases, Mg A ·3THF likely functioned as an outer-sphere two-electron reductant instead of exhibiting the desired “double-Grignard” mode of nucleophilic C–P bond-forming reactivity …”

Section: Resultsmentioning

confidence: 99%

“…2 In these two cases, MgA•3THF likely functioned as an outer-sphere two-electron reductant instead of exhibiting the desired "double-Grignard" mode of nucleophilic C−P bond-forming reactivity. 21 The parent derivative H 2 NPA could not be accessed directly from MgA•3THF and a dichlorophosphine due to the unavailability of H 2 NPCl 2 . Instead, ClPA, produced from Me 2 NPA and ethereal hydrogen chloride, 19 was found to react with excess ammonia in dioxane solution to yield H 2 NPA in 55% yield.…”

Section: ■ Introductionmentioning

confidence: 99%

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Mechanism and Scope of Phosphinidene Transfer from Dibenzo-7-phosphanorbornadiene Compounds

et al. 2017

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Dibenzo-7-phosphanorbornadiene compounds, RPA (A = CH or anthracene), are investigated as phosphinidene sources upon thermally induced (70-90 °C) anthracene elimination. Analysis of substituent effects reveals that π-donating dialkylamide groups are paramount to successful phosphinidene transfer; poorer π-donors give reduced or no transfer. Substituent steric bulk is also implicated in successful transfer. Molecular beam mass spectrometry (MBMS) studies of each derivative reveal dialkylamide derivatives to be promising precursors for further gas-phase spectroscopic studies of phosphinidenes; in particular, we present evidence of direct detection of the dimethylamide derivative, [MeN═P]. Kinetic investigations of PrNPA thermolysis in 1,3-cyclohexadiene and/or benzene-d are consistent with a model of unimolecular fragmentation to yield free phosphinidene [PrN═P] as a transient reactive intermediate. This conclusion is probed by density functional theory (DFT) calculations, which favored a mechanistic model featuring free singlet aminophosphinidenes. The breadth of phosphinidene acceptors is expanded to unsaturated substrates beyond 1,3-dienes to include olefins and alkynes; this provides a new synthetic route to valuable amino-substituted phosphiranes and phosphirenes, respectively. Stereoselective phosphinidene transfer to olefins is consistent with singlet phosphinidene reactivity by analogy with the Skell hypothesis for singlet carbene addition to olefins.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Mechanism and Scope of Phosphinidene Transfer from Dibenzo-7-phosphanorbornadiene Compounds

et al. 2017

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“…8 We found that oxidation with peroxides at low temperatures ( -15°C) gave, as the first recognizable product, l-phenylphosphonin oxide (3) with one trans-double bond. Apparently the increase in coordination of phosphorus in going from 1 to its oxide 2 created additional strain in the 3-membered ring, rendering it unstable even at -15OC.…”

Section: -Thlasteroldmentioning

confidence: 85%

Comparative Studies on Synthesis and Properties of Phosphorus and Sulfur Heterocycles: The Heteronin Oxide System

Quin

Rao

Szewczyk

1986

Phosphorous and Sulfur and the Related Elements

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“…B. auch das erste bei Raumtemperatur stabile Derivat, 1-tert-Butyl-2-methyl-phosphiran, durch M. Baudler et al im Jahre 1978 dargestellt werden [5]. Neben bicyclischen Phosphiranen, die seit 1966 be-kannt sind [6], ru È ckten gerade auch in ju È ngster Vergangenheit polycyclische Phosphirane [7] und ihre Metallkomplexe [8] in den Blickpunkt des Interesses, da bei ihnen ungewo È hnliche Ligandeigenschaften zu vermuten sind [9] und mittlerweile auch einige Belege dafu È r vorliegen [10]. Auch die seit 1971 [11] bekannten Pentacarbonylmetallkomplexe sind wegen ihres hohen Synthesepotentials von speziellem Interesse [2,3], und ko È nnen z.…”

Section: Introductionunclassified

Synthese und spektroskopische Charakterisierung einiger Pentacarbonylwolfram(0)-Komplexe mit monound bicyclischen Phosphiran-Liganden: Kristallstruktur von [{(Me3Si)2HCPC(H)H-C(H)Ph}W(CO)5]

Ostrowski

Jeske

Jones

et al. 2001

Z. anorg. allg. Chem.

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Frau Professor Marianne Baudler zum 80. Geburtstag gewidmet Inhaltsu È bersicht. Der Wolfram(0)-Komplex [{(Me 3 Si) 2 -HCPC(Ph)=N}W(CO) 5 ](1) reagiert beim Erwa Èrmen mit den Alkenderivaten 2, 6, 8, und 10 in Toluol zu Benzonitril und den Komplexen [{(Me 3 Si) 2 HCPC(R 1 ,R 2 )±C(R 3 ,R 4 }-W(CO) 5 ] (4, 7 a, b, 9 a, b, 11 a, b) (4 (trans): R 1 ,R 3 = Ph, R 2 ,R 4 = H, 7 a, b (cis; meso und rac): R 1 ,R 3 = Ph, R 2 ,R 4 = H, 9 a, b (RR und SS): R 1 = Ph, R 2 ,R 3 ,R 4 = H, 11 a, b: R 1 =R 3 = (CH 2 ) 4 , R 2 ,R 4 = H). Spektroskopische und massen-spektrometrische Daten werden angegeben und diskutiert. Die Struktur des Komplexes 9 a konnte durch Einkristall-Ro È ntgenstrukturanalyse aufgekla È rt werden, wobei der spitze Winkel am Phosphor-Atom (49,2(2)°), die verschiedenen P±C-Absta È nde (P±C (6) 182,1(5) und P±C (7) 185,2(4) pm) sowie 152,9(6) pm fu È r die basale C±C-Bindung als charakteristische Strukturmerkmale des Phosphiran-Rings zu nennen sind.Abstract. The tungsten (0) complex [{(Me 3 Si) 2 -HCPC(Ph)=N}W(CO) 5 ] (1) reacts upon heating with alkene derivatives 2, 6, 8, and 10 in toluene to form benzonitrile and the complexes [{(Me 3 Si) 2 HCPC(R 1 ,R 2 )±C(R 3 ,R 4 }W(CO) 5 ](4, 7 a, b, 9 a, b, 11 a, b) (4 (trans): R 1 ,R 3 = Ph, R 2 ,R 4 = H, 7 a, b (cis, meso and rac): R 1 ,R 3 = Ph, R 2 ,R 4 = H, 9 a, b (RR und SS): R 1 = Ph, R 2 ,R 3 ,R 4 = H, 11 a, b: R 1 =R 3 = (CH 2 ) 4 , R 2 ,R 4 = H). Spectroscopic and mass spectrometric data are discussed. The structure of the complex 9 a was determined by X-ray single crystal structure analysis showing characteristic data for the phosphirane ring such as a narrow angle at phosphorus (49,2(2)°), different P±C distances (P±C(6) 182,1(5) and P±C(7) 185,2(4) pm) and 152,9(6) pm for the basal C±C bond. 9 b: 1 H-NMR: d = 0,33 (s, 9 H, SiMe 3 ), 0,37 (s, 9 H, SiMe 3 ), 1,74 (m c , 2H, PCH + PCHPh), 2,95 (m c , 2 H, PCH 2 ), 7,28 (m c , 5 H, Ph). 13 C{ 1 H}-NMR:

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The Reaction of Dipotassium Cyclooctatetraenide with Dichlorophenylphosphine. Rearrangements of 9-Phenyl-9-phosphabicyclo[6.1.0]nonatriene and 9-Phenyl-9-phosphabicyclo[4.2.1]nonatriene

Cited by 73 publications

References 0 publications

Mechanism and Scope of Phosphinidene Transfer from Dibenzo-7-phosphanorbornadiene Compounds

Mechanism and Scope of Phosphinidene Transfer from Dibenzo-7-phosphanorbornadiene Compounds

Comparative Studies on Synthesis and Properties of Phosphorus and Sulfur Heterocycles: The Heteronin Oxide System

Synthese und spektroskopische Charakterisierung einiger Pentacarbonylwolfram(0)-Komplexe mit monound bicyclischen Phosphiran-Liganden: Kristallstruktur von [{(Me3Si)2HCPC(H)H-C(H)Ph}W(CO)5]

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