Bis[cyclotri(λ5‐phosphazan)dienthionato]‐NiII, PdII, xk PtII‐Komplexe und ihre Struktur[1]

Schmidpeter, Alfred; Blanck, Klaus; Ahmed, F. R.

doi:10.1002/ange.19760881504

Cited by 8 publications

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“…Im Anschluß an die Darstellung von Phosphino- [3] und Phosphinylcyclotri(phosphazenen) [4] aus dem [6,7]. Dieses Ergebnis läßt zunächst an eine einfache Schwefelübertragung von 2 auf 1 [7] denken.…”

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Phosphoraustausch im Cyclophosphazenring bei der Reaktion Hydridocyclotri(phosphazen)/Perthiophosphonsäureanhydrid [1] / Exchange of Phosphorus in the Cyclophosphazene Ring in the Reaction Hydridocyclotri (phosphazene )/Perthiophosphonic Anhydride [1]

Högel¹,

Schmidpeter²

1979

Zeitschrift Für Naturforschung B

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Abstract The 2-hydrido-2-methyl-cyclotri(phosphazene) (1) reacts with perthiophosphonic anhydrides (2) to give cyclotri(phosphazene)diene-2-thiones (3). When 2 contains R ≠ CH3, mixtures of CH3-3 and R-3 are obtained. This must be due to a competition of sulfur transfer from 2 to 1 and the insertion of a RPS unit from 2 into 1 involving the opening and reclosure of the N3P3 ring. The unusual lability of the cyclotri (phosphazene) ring probably arises from the prototropy in 1

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“…Dieses Ergebnis läßt zunächst an eine einfache Schwefelübertragung von 2 auf 1 [7] denken. Es zeigt sich aber, daß man nur aus der Experimenteller Teil (1, C2H5 statt CH3) [5,8] …”

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Phosphoraustausch im Cyclophosphazenring bei der Reaktion Hydridocyclotri(phosphazen)/Perthiophosphonsäureanhydrid [1] / Exchange of Phosphorus in the Cyclophosphazene Ring in the Reaction Hydridocyclotri (phosphazene )/Perthiophosphonic Anhydride [1]

Högel¹,

Schmidpeter²

1979

Zeitschrift Für Naturforschung B

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Über Phosphazene, 62: Phosphino‐cyclotri(phosphazene)

Schmidpeter

Högel

1978

Chem. Ber.

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Das Hydrido-cyclotri(phosphazen) 1 addiert Chlorphosphine 2 unter PP-Verkniipfung zu Hydrochloriden 3 von Phosphino-cyclotri(phosphazenen) 6, aus denen mit NH, diese selbst freigesetzt werden konnen. -Mit dem bifunktionellen Dichlormethylphosphin (9) und auch rnit Tris(dimethy1amino)phosphin kommt eine PPP-Verkniipfung zweier Phosphazenringe iiber eine Phosphinobriicke zustande.Phosphazenes, 62" Phosphino-cyclotri(phosphazenes)The hydrido-cyclotri(phosphazene) 1 adds chlorophosphines 2 by PP-linking to hydrochlorides 3 of phosphino-cyclotri(phosphazenes) 6 which can be deprotonated to 6 by NH,. -In the reactions of I with bifunctional dichloromethylphosphine (9) and also with tris(dimethy1amino)phosphine a PPP-chain is formed to connect two phosphazene rings by a phosphino bridge.Hydrido-cyclotri(ph0sphazene) reagieren auch ohne Katalyse mit einer Vielfalt von Elektrophilen '). Unter Verdrangen des Protons tritt das Elektrophil dabei stets an den Phosphor. Mit Chlor-und Aminophosphinen werden auf diesem Weg nun erstmalig Phosphino-cyclophosphazene zuganglich. Sie stellen -anders gesehen -einen Sonderfall der Biphosphin-monimine (und Triphosphin-diimine) dar. PP-VerkniipfungenAls Hydrido-cyclotri(phosphazen) diente das 2-Methyl-4,4,6,6-tetraphenyl-Derivat 1.Es vereinigt sich mit den Chlorphosphinen 2 zu den Phosphino-cyclotri(phosphazen)iumchloriden 34). Umsetzung und Aufarbeitung miissen dabei zum Teil unterhalb Raumtemperatur durchgefiihrt werden, da Chlorphosphine -wie schon friiher beobachtet -7, -61. Mitteil.: A . Schmidpeter und Th. u. Criegern, J. Chem. SOC., Chem. Commun. 1978,470.

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Phosphazenes with (2‐Pyridylmethylamino) Groups, I. Syntheses and Crystal Structures of Pentaphenoxy(2‐pyridylmethylamino)‐cyclotriphosphazene and Its Copper(II) Nitrate, Platinum (II) Chloride, and Cobalt(II) Nitrate Complexes

1996

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The reaction of the (2-pyridylmethylamino)-substituted cyclotriphosphazene N3P3(0C6H5)5(NHCH2(C5H4N)-2) (1) with copper(I1) nitrate, platinum(I1) chloride, and cobalt(I1) nitrate yields the stable complexes [Cu(N03), .( 1 ) 4 (la), [PtQ . (l)] ( l b ) , [CO(NO,)~ . ( l ) ] ( l c ) . The X-ray crystallographic studies of these metal complexes revealed the different coordination behavior of the multifunctional ligand.Since the last decades the interest in polymers which form macromolecular metal complexes has been increasing significantly because of the wide range of possible applications for these materials such as ion exchange resins, catalysts, ionic conductors, and carriers or depots for chemotherapeutic For these applications not only the knowledge of the structures of the metal centers but also the physical properties of the polymeric complexes are important for fundamental mechanistical reason^[^^']. Small molecular modelling offers the opportunity to gain important information about the coordination behavior of the functional sites in macromolecules. This method is well established in phosphazene chemistry [2]. Cyclic phosphazene trimers are, besides their importance in the fundamental research of this class of compounds, indicators for the structural and chemical behavior of analogous macromolecules. Especially the coordination behavior of cyclotriphosphazenes can be studied by X-ray crystallography.In the past, different side groups which interact with transition metals were described. Previous choices of exocyclic coordination groups include, for example, phosphanes, acetylenic units, or aryl g r o u p~ [~~~] .These groups are bound to the metal by P-or n-donor coordination.Another type of exocyclic side groups are N-donor groups such as pyrazolyl or dimethylamino groups. This kind of phosphazene contains two possible coordination sites which can interact with transition metals: (a) The Ndonor side group reacts preferably, when electron-withdrawing groups such as pyrazolyl or imidazolyl are combined with phenyl, phenoxy, or trifluoroethoxy Pyridine-substituted phosphazenes are rare, mainly because reactions of chlorinated phosphazenes with pyridine derivatives are known to form cationic adducts which decompose rapidly when water, even in traces, is present in the reaction rnixt~re[~~~'*]. Studies of the complex formation of these phosphazene derivatives are hardly known, and no molecular structures of metal complexes have been published so far [19~20].We recently described the synthesis of several pyridylalkylamino-substituted cyclo-and polyphosphazenes[21 -231. 2-(Aminomethy1)pyridine is known to react with transition metal ions as a bidentate chelating ligand1241. Once attached to the phosphazene, the three PN nitrogen atoms might additionally participate in complex formation although the possibility of metal interactions at these sites is quite low when cosubstituents lower their basicity.Our latest experiments revealed that the new phosphazene-based N-donor ligand shows a very interesting coordin...

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Bis[cyclotri(λ⁵‐phosphazan)dienthionato]‐Ni^II, Pd^II, xk Pt^II‐Komplexe und ihre Struktur^[1]

Cited by 8 publications

References 1 publication

Phosphoraustausch im Cyclophosphazenring bei der Reaktion Hydridocyclotri(phosphazen)/Perthiophosphonsäureanhydrid [1] / Exchange of Phosphorus in the Cyclophosphazene Ring in the Reaction Hydridocyclotri (phosphazene )/Perthiophosphonic Anhydride [1]

Phosphoraustausch im Cyclophosphazenring bei der Reaktion Hydridocyclotri(phosphazen)/Perthiophosphonsäureanhydrid [1] / Exchange of Phosphorus in the Cyclophosphazene Ring in the Reaction Hydridocyclotri (phosphazene )/Perthiophosphonic Anhydride [1]

Über Phosphazene, 62: Phosphino‐cyclotri(phosphazene)

Phosphazenes with (2‐Pyridylmethylamino) Groups, I. Syntheses and Crystal Structures of Pentaphenoxy(2‐pyridylmethylamino)‐cyclotriphosphazene and Its Copper(II) Nitrate, Platinum (II) Chloride, and Cobalt(II) Nitrate Complexes

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