Synthesis of Cyclo- and Polyphosphazenes with Pyridine Side Groups

Diefenbach, Ursula; Allcock, Harry R.

doi:10.1021/ic00098a024

Cited by 25 publications

(20 citation statements)

References 6 publications

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“…They are usually regarded as an electron-donating group because of their similarity to the alkoxy or thioalkoxy groups, [4] but they can also act as an electron-withdrawing group depending on the nature of the group connected to these substituents. [5] In the present case, electrochemical studies showed that the introduction of eight phenoxy or thiophenoxy groups on the peripheral positions of the phthalocyaninato ligands slightly hinders the oxidation and facilitates the reduction of the resulting double-decker complexes. Similar results have also been previously observed for the metal-free 2(3),9(10), 16(17),23(24)-tetraphenoxyphthalocyanine and 2,3,9,10,16,17,23,24-octaphenoxyphthalocyanine.…”

Section: Introductionmentioning

confidence: 55%

Lanthanide(III) Double‐Decker Complexes with Octaphenoxy‐ or Octathiophenoxyphthalocyaninato Ligands – Revealing the Electron‐Withdrawing Nature of the Phenoxy and Thiophenoxy Groups in the Double‐Decker Complexes

Bai

et al. 2006

Eur J Inorg Chem

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Section: Introductionmentioning

confidence: 55%

Lanthanide(III) Double‐Decker Complexes with Octaphenoxy‐ or Octathiophenoxyphthalocyaninato Ligands – Revealing the Electron‐Withdrawing Nature of the Phenoxy and Thiophenoxy Groups in the Double‐Decker Complexes

Bai

et al. 2006

Eur J Inorg Chem

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“…These incorporate primary alkyl-or arylamines, imidazole, isothiocyanates, thiourethanes, thioureas, pyrrole, or pyridine side units. [18][19][20][21][22][23][24][25] However, phosphazenes with aliphatic tertiary amines, specifically -OCH 2 -CH 2 N(CH 3 ) 2 , in the side group structure have been limited to mixed-substituent materials with less than 20% of the side groups bearing the tertiary amine, and this undoubtedly disguised some of the problems that became apparent in the present work. 26,27 The incorporation of tertiary amino units into the side groups of polyphosphazenes can, in principle, be accomplished through reaction of a chlorophosphazene such as 2 with an alkoxide, aryloxide, primary amine, or secondary amine that bears a tertiary amino residue, typically at the terminus of the reagent.…”

Section: Introductionmentioning

confidence: 85%

Functionalized Polyphosphazenes: Polymers with Pendent Tertiary Trialkylamino Groups

et al. 1998

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Attempts have been made to synthesize polyphosphazenes with pendent tertiary amino side units via macromolecular substitution. Incorporation of -OCH2CH2N(CH3)2, -OCH2CH2OCH2-CH2N(CH3)2, and -NHCH2CH2N(CH3)2 groups was studied. Polymers in which all the side groups consisted of one type of aliphatic tertiary amino-containing unit and species that also contained 2,2,2-trifluoroethoxy or phenoxy groups as cosubstituents were examined. Related phosphazene cyclic trimers were also prepared as small molecule model systems to examine synthetic variables, characterization techniques, and hydrolytic behavior. Those phosphazenes in which the tertiary amino-containing side groups are linked to the skeleton through an aliphatic oxygen-phosphorus bond are sensitive to hydrolysis induced by the basicity of the terminal amino group. However, species in which the tertiary aminocontaining units are linked to the backbone through an alkyl nitrogen-phosphorus bond are stable to water and are candidate materials for use in a range of membrane and surface applications. Small molecule model studies also identified reactions of P-Cl bonds in (NPCl2)3 with N,N-dimethylbutylamine to form dialkylamino-substituted phosphazenes and hydrolysis products.

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“…Ûber die Synthese von 2-(2-(2-Pyridyl)ethylamino) 4,4,6,4k 5 ,3,4,4,6,4k 5 ,3,5trien (2) haben wir bereits berichtet [11,20].…”

Section: Strukturuntersuchungen Und Komplexbildung Von Monofunktionalunclassified

Synthese, Komplexbildung und Kristallstrukturen von Cyclotriphosphazenen mit Pyridylalkylaminogruppen

Bloy

Kretschmann

Scholz

et al. 2000

Z. anorg. allg. Chem.

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Cobalt(II)chlorid fu È hrt zum Cobaltkomplex (2 a), in dem zwei Moleku È le des Liganden durch die Pyridinstickstoffatome an das tetraedrisch koordinierte Cobaltatom gebunden sind. Der tetrafunktionalisierte Ligand gem-N 3 P 3 (OC 6 H 5 ) 2 (NHCH 2 CH 2 C 5 H 4 N-2) 4 (8) reagiert mit Cobalt(II)chlorid zu einem zweikernigen Cobalt±Cobaltat Komplex (8 a). Die CoCl-Einheit ist hier durch Wechselwirkungen eines Phosphazenstickstoffatoms und zweier Pyridingruppen cis-vicinal angeordneter Substituenten gebunden, wa È hrend die CoCl 3 -Gruppe mit einer weiteren Pyridineinheit verknu È pft ist. Synthesis, Complex Formation and Crystal Structures of Cyclotriphosphazenes with Pyridylalkylamino GroupsAbstract. A variety of cyclotriphosphazenes with different numbers and types of functional pyridylalkylamino groups were synthesized by reactions of chlorophosphazenes with aminoalkylpyridine derivatives and completely characterized. The molecular structures of one multifunctional N-donor ligand, N 3 P 3 (OC 6 H 5 ) 5 (NHCH 2 CH 2 C 5 H 4 N-2) (1), was determined by X-ray structure analysis. The hexafunctionalized derivative N 3 P 3 (NHCH 2 CH 2 C 5 H 4 N-2) 6 (10) reacts with dichloromethane to form the HCl salt (10 a) the structure of which could also determined by X-ray crystal structure analysis. Complex formation of N 3 P 3 (OC 6 H 5 ) 5 (NHCH 2 C 5 H 4 N-3) (2) with cobalt(II) chloride yields the cobalt complex (2 a) in which two molecules of the ligand are bonded to the tetrahedraly coordinated cobalt atom by the pyridine nitrogen atoms. The tetra functionalized ligand gem-N 3 P 3 (OC 6 H 5 ) 2 -(NHCH 2 CH 2 C 5 H 4 N-2) 4 (8) forms the dinuclear cobalt-cobaltate complex (8 a) by interactions of a phosphazene nitrogen atom and the pyridine atoms of two cis-vicinal functional groups with a CoCl unit and a pyridine group with a CoCl 3unit.

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Synthesis of Cyclo- and Polyphosphazenes with Pyridine Side Groups

Cited by 25 publications

References 6 publications

Lanthanide(III) Double‐Decker Complexes with Octaphenoxy‐ or Octathiophenoxyphthalocyaninato Ligands – Revealing the Electron‐Withdrawing Nature of the Phenoxy and Thiophenoxy Groups in the Double‐Decker Complexes

Lanthanide(III) Double‐Decker Complexes with Octaphenoxy‐ or Octathiophenoxyphthalocyaninato Ligands – Revealing the Electron‐Withdrawing Nature of the Phenoxy and Thiophenoxy Groups in the Double‐Decker Complexes

Functionalized Polyphosphazenes: Polymers with Pendent Tertiary Trialkylamino Groups

Synthese, Komplexbildung und Kristallstrukturen von Cyclotriphosphazenen mit Pyridylalkylaminogruppen

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