Synthesis and electrochemistry of polymeric complexes with cationic manganese carbonyl fragments coordinated to polyphosphazenes through nitrile ligands

Carriedo, Gabino A.; Fernández‐Catuxo, Lucia; Alonso, Francisco; Gómez‐Elipe, Paloma

doi:10.1016/0022-328x(95)05540-6

Cited by 18 publications

(1 citation statement)

References 22 publications

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“…A variety of synthetic procedures are available for the construction of cyclophosphazenes containing organometallic and other metal-containing pendant groups. , The stability of the cyclophosphazene unit to redox processes allows for utilization of redox active substituents without disruption of the core inorganic ring system. Examples of substituents which undergo oxidation−reduction without phosphazene degradation include cobalt and manganese carbonyls as well as platinum and ferrocene , containing species. A wide number of other cyclophosphazenes with various organometallic substituents 2 also have the potential for redox activity.…”

Section: Introductionmentioning

confidence: 99%

N-(Ferrocenylmethyl)-N-methylaminocyclotriphosphazenes

Myer

Allen

2001

Inorg. Chem.

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The reactions of N-(ferrocenylmethyl)-N-methylamine, C(5)H(5)FeC(5)H(4)CH(2)(Me)NH, with hexachlorocyclotriphosphazene, N(3)P(3)Cl(6), led to the formation of the N-(ferrocenylmethyl)-N-methylaminocyclotriphosphazene derivatives, N(3)(-)P(3)Cl(6-n)[N(Me)CH(2)C(5)H(4)FeC(5)H(5)](n) (n = 1-3). Only small amounts of higher degrees of substitution could be detected. In the case of the disubstituted products, the ratio of isomers was dependent on the polarity of the solvent. In nonpolar solvents the ratio was trans > geminal > cis while in acetonitrile only equal amounts of trans and cis isomers were observed. The reaction of N-(ferrocenylmethyl)-N-methylamine with (methacryloylbutenedioxy)pentachlorocyclotriphosphazene, N(3)P(3)Cl(5)O(CH(2))(4)OC(O)C(Me)=CH(2), gives the surprising geminal isomer 2,2-N(3)P(3)Cl(4)[O(CH(2))(4)OC(O)C(Me)=CH(2)]N(Me)CH(2)C(5)H(4)FeC(5)H(5) and the tris derivative 2,2',4-N(3)P(3)Cl(3)[O(CH(2))(4)OC(O)C(Me)=CH(2)][N(Me)CH(2)C(5)H(4)FeC(5)H(5)](2). All of the phosphazene derivatives were characterized by elemental analyses, mass spectrometry, IR and NMR ((1)H, (13)C, (31)P) spectroscopy, and electrochemical techniques (cyclic, normal pulse, and differential pulse voltametry). The compounds all undergo a single, reversible oxidation reduction process.

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Section: Introductionmentioning

confidence: 99%

N-(Ferrocenylmethyl)-N-methylaminocyclotriphosphazenes

Myer

Allen

2001

Inorg. Chem.

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Synthesis and1H-,15N-,31P-,183W-Multinuclear Magnetic Resonance Study of the Cyclotriphosphazenes [N3P3(dobp)2(OC5H4N-4)2] and [N3P3(dobp)(OC5H4N-4)4] and Their W(CO)5 Complexes (dobp = 2,2′-dioxybiphenyl)

Carriedo

Alonso

Garcı́a

et al. 1999

Eur. J. Inorg. Chem.

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The reactions of [N3P3(dobp)2Cl2] and [N3P3(dobp)Cl4] with a mixture of HOC5H4N‐4 and K2CO3 in acetone give the cyclotriphosphazenes [N3P3(dobp)2(OC5H4N‐4)2] and [N3P3(dobp)(OC5H4N‐4)4], respectively. These compounds react with [W(MeOH)(CO)5] in methanol to give mixtures of the polymetallic complexes [N3P3(dobp)2(OC5H4N‐4)2{W(CO)5}x] (x = 1, 2) and [N3P3(dobp)(OC5H4N‐4)4{W(CO)5}x] (x = 1–4), which are unstable in solution, slowly undergoing loss of the pentacarbonyl moiety. A complete characterization by multinuclear 1H, 15N, 31P, 183W magnetic resonance has revealed that the complexation of the N atom of one 4‐oxypyridine ligand by the W(CO)5 fragment has a measurable effect on other parts of the phosphazene molecule very far away from the coordination site. The changes observed in δ183W have been used to identify the components in mixtures of compounds incorporating different numbers of tungsten atoms in the molecule. The characterization of less sensitive nuclei has been accomplished by means of indirect detection methods.

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