“…Phosphor(III)adamantane 573 ( n = 2) reacts with benzil to give the spirophosphorane 574 . Similarly, 9,10-phenanthrenequinone or 3,5-di- tert -butyl- o -benzoquinone reacts with phosphor(III)adamantanes 573 ( n = 0, 1, 2, 6) to produce the corresponding phosphoranes 575 . , …”
Section: Reactions With Heterocyclic Phosphorus
Compoundsmentioning
confidence: 99%
“…Hexafluorobiacetyl reacts very rapidly with 1-phospha-2,8,9-trioxaadamantane ( 578 ) to give the caged polycyclic pentaoxyphosphorane 579 . From its 1 H, 19 F, and 31 P NMR studies, the oxyphosphorane is formulated as trigonal bipyramids with the five-membered ring in an apico−equatorial skeletal position and with the ligands undergoing a relatively rapid exchange among the skeletal positions by the intramolecular mechanism termed the “turnstile rotation”. ,− Also, the spirophosphoranes 580 [R 1 = t -Bu, R 2 = H; R 1 R 2 = (CH) 4 ] are formed from the reaction of phosphore(III)adamantane 578 with 3,5-di- tert -butyl- o -benzoquinone and 9,10-phenanthrenequinone …”
Section: Reactions With Heterocyclic Phosphorus
Compoundsmentioning
confidence: 99%
“…Similarly, 9,10-phenanthrenequinone or 3,5-di-tert-butyl-o-benzoquinone reacts with phosphor(III)adamantanes 573 (n ) 0, 1, 2, 6) to produce the corresponding phosphoranes 575. 384 On the other hand, treating 3,5-di-tert-butyl-obenzoquinone with phosphor(III)adamantane 576 gives the hexacoordinated product 577. 385 Hexafluorobiacetyl reacts very rapidly with 1-phospha-2,8,9-trioxaadamantane (578) to give the caged polycyclic pentaoxyphosphorane 579.…”
Section: Reactions With Heterocyclic Phosphorus Compoundsmentioning
“…Phosphor(III)adamantane 573 ( n = 2) reacts with benzil to give the spirophosphorane 574 . Similarly, 9,10-phenanthrenequinone or 3,5-di- tert -butyl- o -benzoquinone reacts with phosphor(III)adamantanes 573 ( n = 0, 1, 2, 6) to produce the corresponding phosphoranes 575 . , …”
Section: Reactions With Heterocyclic Phosphorus
Compoundsmentioning
confidence: 99%
“…Hexafluorobiacetyl reacts very rapidly with 1-phospha-2,8,9-trioxaadamantane ( 578 ) to give the caged polycyclic pentaoxyphosphorane 579 . From its 1 H, 19 F, and 31 P NMR studies, the oxyphosphorane is formulated as trigonal bipyramids with the five-membered ring in an apico−equatorial skeletal position and with the ligands undergoing a relatively rapid exchange among the skeletal positions by the intramolecular mechanism termed the “turnstile rotation”. ,− Also, the spirophosphoranes 580 [R 1 = t -Bu, R 2 = H; R 1 R 2 = (CH) 4 ] are formed from the reaction of phosphore(III)adamantane 578 with 3,5-di- tert -butyl- o -benzoquinone and 9,10-phenanthrenequinone …”
Section: Reactions With Heterocyclic Phosphorus
Compoundsmentioning
confidence: 99%
“…Similarly, 9,10-phenanthrenequinone or 3,5-di-tert-butyl-o-benzoquinone reacts with phosphor(III)adamantanes 573 (n ) 0, 1, 2, 6) to produce the corresponding phosphoranes 575. 384 On the other hand, treating 3,5-di-tert-butyl-obenzoquinone with phosphor(III)adamantane 576 gives the hexacoordinated product 577. 385 Hexafluorobiacetyl reacts very rapidly with 1-phospha-2,8,9-trioxaadamantane (578) to give the caged polycyclic pentaoxyphosphorane 579.…”
Section: Reactions With Heterocyclic Phosphorus Compoundsmentioning
“…[31,32] A variety of lower-rim (C 3 N 3 ring) modified derivatives have been published involving opening of the cage, [21,22,23,25,27,33] expansion of the ring, [34,35] substitution of a methylene with SO 2 , [24,36] or trisubstitution of the triazacyclohexane ring. [19] Upper-rim derivatives of PTA have been synthesized by addition of aldehydes, ketones, imines, and carbon dioxide to lithiated PTA (PTA-Li) resulting in the formation of carboxylates, [20] β-phosphino alcohols, [20,28,30] or β-amino phosphines; [10] Scheme 1.…”
Please cite this article as: J.M. Sears, W-C. Lee, B.J. Frost, Water Soluble Diphosphine ligands based on 1,3,5-triaza-7-phosphaadamantane (PTA-PR 2 ): synthesis, coordination chemistry, and ruthenium catalyzed nitrile hydration, Inorganica Chimica Acta (2015), doi: http://dx.ABSTRACT: Two chiral chelating 1,3,5-triaza-7-phosphaadamantane (PTA) derivatives were synthesized, in racemic form, by addition of ClP i Pr 2 or ClP(N i Pr) 2 (CH 2 ) 2 to lithiated PTA. PTA-P i Pr 2 (1) and PTA-P(N i Pr) 2 (CH 2 ) 2 (2) were isolated in good yield, 73 % and 56 % respectively, and fully characterized by multinuclear NMR spectroscopy, mass spectrometry, and X-ray crystallography. PTA-P i Pr 2 is highly air sensitive, but stable and somewhat soluble in degassed water. PTA-P(N i Pr) 2 (CH 2 ) 2 (2) is air-stable, but decomposes in water over the course of hours. Two tungsten tetracarbonyl complexes were prepared by addition of the PTA-PR 2 to [W(CO) 4 (pip) 2 ] and characterized by NMR and IR spectroscopies and X-ray crystallography in the case of [W(CO) 4 (PTA-P i Pr 2 )]. Based on IR spectroscopy PTA-P i Pr 2 (1) is more electron donating than PTA-P(N i Pr) 2 (CH 2 ) 2 (2) or the previously published PTAPPh 2 . Products isolated from the reaction of [(η 6 -toluene)RuCl 2 ] 2 with two equivalents of 1 were found to contain monodentate (κ 1 ), bidentate (κ 2 ), and possibly bridging coordination modes of PTA-P i Pr 2 . These ruthenium complexes were explored as catalysts for aqueous phase nitrile hydration. Of the ruthenium explored [(η 6 -toluene)RuCl 2 (κ 1 -PTA-P i Pr 2 )] (7) was the most active towards nitrile hydration. In the presence of air at 100 °C 7 converted various nitriles to the respective amides with 43-99% conversions in 7 h.
“…53 Addition of a-quinone leads to the corresponding Pv derivative 34 (Scheme 18). 54 Macrocycles comprising alternating phosphorus atoms and alkyne units 35 and 36 are elegantly prepared by treatment of fert-butyldiethynylphosphine or 3,6di-tert-butyl-3,6-diphospha-l,4,7-octatriyne with ethylmagnesium bromide followed by addition of tertbutyldichlorophosphine (Scheme 19). 66 Reaction of a 1:4 (molar) mixture of tetrakis[[(phenylsodio)phosphino] methyl] methane (37) (38).…”
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