Synthesis, structure and complexes of a new bicyclic N,P-ligand derived from phosphatriazaadamantane

Assmann, Bernd; Angermaier, Klaus; Schmidbaur, Hubert

doi:10.1039/c39940000941

Cited by 27 publications

(12 citation statements)

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“…The decomposition of a bis-PTN(Me) silver complex, 1a was monitored over several weeks using 31 P{ 1 H} NMR spectroscopy and revealed several emerging compounds with the principal species being tentatively assigned as the P-oxide of PTN(Me), which has a deshielded signal of 4.85 ppm, a region typically associated with phosphine oxides, i.e., P-oxide of PTA δ( complexes. 20 Interestingly, the greater liability of the PTN(Me) ligand in the tris-coordinated complexes can be demonstrated by reacting 2a with half an equivalent of silver acetate in D 2 O, as the bis-PTN(Me) complex 1a was quatitative formed as indicated through 31 P{ 1 H} NMR.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Employing sodium as the reducing reagent converts P-methyl-PTA + into PTN(Me) via cleavage of a phosphorus–carbon bond (Scheme ). The reaction is not entirely selective, and PTA is also formed as a coproduct, but PTN(Me) is easily separated through low temperature, static vacuum sublimation. PTN(Me) has a bulkier structure than the closed structure analogue PTA, with a methyl functionality both on the phosphorus and terminal nitrogen center.…”

Section: Introductionmentioning

confidence: 99%

“…19 A previously reported upper and lower rim modified version of PTA is 7-phospha-3,7-dimethyl-1,3,5-triazabicyclo[3.3.1]nonane (herein abbreviated as PTN) was first described by Schmidbaur and is the subject of this report. 20 The synthetic route first requires the cyclization of tris-P-hydroxymethyl-Pmethyl phosphonium salt to afford a P-methyl substituted PTA salt, followed by Birch reduction conditions. Employing sodium as the reducing reagent converts P-methyl-PTA + into PTN-(Me) via cleavage of a phosphorus−carbon bond (Scheme 1).…”

Section: ■ Introductionmentioning

confidence: 99%

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Water-Soluble Silver(I) Complexes Featuring the Hemilabile 3,7-Dimethyl-1,3,5-triaza-7-phosphabicyclo[3.3.1]nonane Ligand: Synthesis, Characterization, and Antimicrobial Activity

Armstrong¹,

Kirk²,

Murphy³

et al. 2018

Inorg. Chem.

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This paper describes the preparation and comprehensive characterization of a series of water-soluble cationic silver(I)-centered complexes featuring the hemilabile P, N-ligand known as 3,7-dimethyl-1,3,5-triaza-7-phosphabicyclo[3.3.1]nonane (herein abbreviated as PTN(Me)) and differing types of monoanionic counterions including known biologically active sulfadiazine and triclosan. The complexes primarily differed though the number of coordinating PTN(Me) ligands. The bis-substituted Ag(I) complexes revealed P, N bidentate coordination, while the only P-monocoordination of the metal center was observed for the tris-substituted systems. The bis-ligated silver compounds were observed to quickly degrade upon photoexposure or in contact with air. In contrast, the tris-ligated complexes demonstrated greater stability, in particular, a high resistance to photo-decomposition. Calculated geometry optimized models using the density functional theory method (BP86) revealed for the bis-substituted PTN(Me) Ag(I) species that the total enthalpy of the tetrahedral C-symmetric structure is marginally lower by -0.6 kcal mol compared to the planar C structure, which is analogous for the corresponding [Au(PTN(Me))] complex with Δ H = -0.5 kcal mol. Hence both types of complexes feature free rotation of the PTN ligand about the M-P bond axis. This series of Ag(I) and bis-PTN(Me) Au(I) complexes were evaluated using the agar well diffusion test for potential antimicrobial and antifungal activity. The nature of the counterion was found to have a strong correlation with the area of microbiological growth inhibition. Silver(I) complexes bearing the deprotonated triclosan as the counterion demonstrated the greatest activity, with large zones of growth inhibition, with the tris-ligated triclosan complex obtaining of a high clearance of 42 mm against the Gram-negative Escherichia coli. In contrast, the previously reported [Au(PTN(Me))]Cl complex demonstrated activity only against E. coli, which is lower than that observed for the silver(I) PTN(Me) species.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Water-Soluble Silver(I) Complexes Featuring the Hemilabile 3,7-Dimethyl-1,3,5-triaza-7-phosphabicyclo[3.3.1]nonane Ligand: Synthesis, Characterization, and Antimicrobial Activity

Armstrong¹,

Kirk²,

Murphy³

et al. 2018

Inorg. Chem.

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“…[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.…”

Section: Introductionmentioning

confidence: 99%

“…Our group, [10,[18][19][20] and others, [21][22][23][24][25][26][27][28][29][30] have been interested in the development of derivatives of the water-soluble and air-stable phosphine 1,3,5-triaza-7-phosphaadamantane (PTA). [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.…”

Section: Introductionmentioning

confidence: 99%

Water soluble diphosphine ligands based on 1,3,5-triaza-7-phosphaadamantane (PTA-PR2): Synthesis, coordination chemistry, and ruthenium catalyzed nitrile hydration

Sears

Lee

Frost

2015

Inorganica Chimica Acta

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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.

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1,3,5-Triaza-7-phosphaadamantane (PTA)

Gonsalvi

Peruzzini

2010

Encyclopedia of Reagents for Organic Synthesis

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The title compound, bis(1,2-diphenyl-2-sulfanylideneethanethiolato-2 S,S 0 )-(1,3,5-triaza-7-phosphaadamantane-P)cobalt(II) dichloromethane hemisolvate, [Co(pdt) 2 (PTA)]Á0.5C 2 H 4 Cl 2 or [Co(C 14 H 10 S 2 ) 2 (C 6 H 12 N 3 P)]Á0.5C 2 H 4 Cl 2 , contains two phenyldithiolene (pdt) ligands and a 1,3,5-triaza-7-phosphaadamantane (PTA) ligand bound to cobalt with the solvent 1,2-dichloroethane molecule located on an inversion center. The cobalt core exhibits an approximately square-pyramidal geometry with partially reduced thienyl radical monoanionic ligands. The supramolecular network is consolidated by hydrogenbonding interactions primarily with nitrogen, sulfur and chlorine atoms, as well as parallel displaced -stacking of the aryl rings. The UV-vis, IR, and CV data are also consistent with monoanionic dithiolene ligands and an overall Co II oxidation state.

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Synthesis, structure and complexes of a new bicyclic N,P-ligand derived from phosphatriazaadamantane

Abstract: Reductive cleavage of the methylphosphoniatriazaadamantane cation by sodium in liquid ammonia affords the new bicyclic ligand (MeP)(CH2)5N2(NMe) whose structure has been determined from crystals of its 1 : 1 complex with AuCI.

Cited by 27 publications

References 5 publications

Water-Soluble Silver(I) Complexes Featuring the Hemilabile 3,7-Dimethyl-1,3,5-triaza-7-phosphabicyclo[3.3.1]nonane Ligand: Synthesis, Characterization, and Antimicrobial Activity

Water-Soluble Silver(I) Complexes Featuring the Hemilabile 3,7-Dimethyl-1,3,5-triaza-7-phosphabicyclo[3.3.1]nonane Ligand: Synthesis, Characterization, and Antimicrobial Activity

Water soluble diphosphine ligands based on 1,3,5-triaza-7-phosphaadamantane (PTA-PR2): Synthesis, coordination chemistry, and ruthenium catalyzed nitrile hydration

1,3,5-Triaza-7-phosphaadamantane (PTA)

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