<u>The Reactions of Alkynlcyclophosphazenes with Metal Carbonyls</u>

Allen, Christopher W.; Malik, Pauline; Bridges, Alan J.; Desorcie, James L.; Pellon, B.

doi:10.1080/10426509008038996

Cited by 14 publications

(20 citation statements)

References 5 publications

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“…This reaction differs considerably when compared to the reaction of CpCo(CO) 2 with (β-phenylethynyl)pentafluorocyclotriphosphazene, which, although it gave (η 5 -cyclopentadienyl)−[η 4 -1, 3-bis(pentafluorocyclotriphosphazenyl)−2, 4-diphenylcyclobutadiene]cobalt, did not result in the formation of any cobaltametallacycle compounds . Further, under similar reaction conditions, the reaction of diphenylacetylene with η 5 -(MeOC(O)C 5 H 4 )Co(PPh 3 ) 2 gave exclusively (η 5 -(MeOC(O)C 5 H 4 )Co(η 4 -C 4 Ph 4 ) .…”

Section: Resultsmentioning

confidence: 90%

“…Tetrahydrofuran, xylene, and toluene were freshly distilled from sodium benzophenone ketyl under a nitrogen atmosphere and used. Sodium salt of carbomethoxycyclopentadiene, 14 tris(triphenylphosphine)cobalt chloride, 17 and (β-phenylethynyl) pentafluorocyclotriphosphazene 12 were prepared according to literature procedures. Diphenyl acetylene, Dimethyl carbonate, and triphenylphosphine (Aldrich) were used as such.…”

Section: Methodsmentioning

confidence: 99%

“…Allen and co-workers have recently shown that pentafluorophosphazenyl-substituted acetylenes such as F 5 P 3 N 3 C⋮CPh can be interesting reagents for the synthesis of novel fluorophosphazene-derived clusters by their reactions with metal carbonyls such as Co 2 (CO) 8 and Fe 2 (CO) 9 . In a related preliminary communication, they have also shown that reactions of the half-sandwich compound, CpCo(CO) 2 , with F 5 P 3 N 3 C⋮CPh results in a novel fluorophosphazene-substituted cyclobutadiene cobalt sandwich compound, along with a few other phosphazene-derived molecules …”

Section: Introductionmentioning

confidence: 97%

“…11 In a related preliminary communication, they have also shown that reactions of the half-sandwich compound, CpCo(CO) 2 , with F 5 P 3 N 3 CtCPh results in a novel fluorophosphazenesubstituted cyclobutadiene cobalt sandwich compound, along with a few other phosphazene-derived molecules. 12 It has been observed that reactions of the half-sandwich compound CpCo(CO) 2 with disubstituted acetylenes differ significantly when compared to that of phosphine complex CpCo(PPh 3 ) 2 . 13,14 Whereas the former, without exception, results in metallocenes with η 5 -cyclopentadienyl-η 4 -cyclobutadiene groups, the latter has also been found to form PPh 3 stabilized cobaltacyclopentadiene metallacycles, depending upon the reaction conditions and nature of substituents on the alkyne.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and Characterization of Novel Fluorophosphazene-Derived Cobaltacyclopentadienyl Metallacycles: Reagents for Assembly of Aryl-Bridged Fluorophosphazenes

2006

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Reaction of (beta-phenylethynyl)pentafluorocyclotriphosphazene, F5P3N3C identical with CPh, with in situ generated eta5-(MeOC(O)C5H4)Co(PPh3)2 resulted in the formation of two isomers of cobaltacyclopentadienylmetallacycles, (eta(5)-carbomethoxycyclopentadienyl)(triphenylphosphine)-2,5-bis(pentafluorocyclotriphosphazenyl)-3,4-diphenyl cobaltacyclopentadiene (1) and (eta5-carbomethoxycyclopentadienyl)(triphenylphosphine)-2,4-bis(pentafluorocyclotriphosphazenyl)-3,5-diphenyl cobaltacyclopentadiene (2), along with the sandwich compound [eta5-carbomethoxycyclopentadienyl]-[eta4-1,3-bis(pentafluorocyclotriphosphazenyl)-2,4-diphenylcyclobutadiene]cobalt (3). Formation of cobaltacyclopentadienylmetallacycles or cyclobutadienylmetallocene having two fluorophosphazene units on vicinal carbon atoms of the rings was not observed in this reaction. Reaction of 1 with diphenylacetylene resulted in the formation of a novel aryl-bridged fluorophosphazene, 1,4-bis(pentafluorocyclotriphosphazenyl)-2,3,5,6-tetraphenyl benzene (4), and the conversion of cobaltametallacycle to the sandwich compound, [eta5-(MeOC(O)C5H4]Co(eta4-C4Ph4) (5). Reaction of 1 with phenylacetylene resulted in the formation of aryl-bridged fluorophosphazene, 1,4-bis(pentafluorophosphazenyl)-2,3,5,-triphenyl benzene (6). New compounds 1-4 were structurally characterized. In compound 1, the two fluorophosphazene units were oriented in gauche form with respect to each other. However, in compounds 2 and 3, they were eclipsed to each other, and in compound 4, they were oriented anti to each other.

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Section: Resultsmentioning

confidence: 90%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

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Synthesis and Characterization of Novel Fluorophosphazene-Derived Cobaltacyclopentadienyl Metallacycles: Reagents for Assembly of Aryl-Bridged Fluorophosphazenes

2006

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“…Alkyne-derived fluorinated cyclophosphazenes are excellent precursors for realizing a range of phosphazene derivatives with diverse organic substitutents. The synthesis of alkyne-derived cyclophosphazenes, first reported in 1971, was followed by exploration of its chemistry in detail by Allen and others, and they have shown the usefulness of arylethynyl-derived fluoro- and chlorophosphazenes in realizing novel cyclophosphazene-derived triazoles, organocobalt clusters, cobalt sandwich compounds, and cobaltacyclopentadienes; they have also shown their use in realizing multiphosphazenyl assemblies by cycloaddition reactions. , …”

Section: Introductionmentioning

confidence: 99%

Reactions of Alkyne- and Butadiyne-Derived Fluorinated Cyclophosphazenes with Diiron and Dimolybdenum Carbonyls

et al. 2014

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The reaction of (β-phenylethynyl)pentafluorocyclotriphosphazene, [(PhC≡C)(F)PN](PNF2)2, with Fe2(CO)9 in refluxing hexane resulted in five new compounds, namely, [Fe(CO)2{η(2):η(2)-2,4-(P3N3F5)2Ph2C4Fe(CO)3}-μ-CO] (1), [Fe(CO)2{η(2):η(2)-2,5-(P3N3F5)2Ph2C4Fe(CO)3}-μ-CO] (2), [Fe(CO)2{η(5)-2,5-(P3N3F5)2Ph2C4CO}C(Ph)═C(P3N3F5)](3), [Fe(CO)3{η(2):η(2)-2,4-(P3N3F5)2Ph2C4CO] (4), and [Fe(CO)3{η(2):η(2)-2,5-(P3N3F5)2Ph2C4CO] (5). While compounds 1, 2, 4, and 5 have five-membered ferracyclopentadiene or cyclopentadienone rings coordinated to the Fe(CO)3 unit in the η(2):η(2) mode, compound 3 has a 2,5-cyclopentadienone ring attached to an Fe(CO)2(P3N3F5)C═C(Ph) unit, where Fe is η(5)-bonded to the cyclopentadienone ring, and the carbon that is α to the phenyl unit of the Fe(CO)2(P3N3F5)C═C(Ph) group is σ-bonded to the oxygen atom of the cyclopentadienone ring. Formation of five-membered cyclic compounds having two fluorophosphazene units on the vicinal carbon atoms of C4R2R'2Y rings was not observed in this reaction. No examples of Fe(CO)3-bound cyclobutadiene complexes were also isolated from this reaction. A similar reaction in the presence of trimethylamine N-oxide, NMe3O, was found to proceed at -20 °C with the formation of compounds 4 and 5 only. In contrast to the Fe2(CO)9 reaction, a reaction of alkyne-derived pentafluorocyclotriphosphazenes, [(RC≡C)(F)PN](PNF2)2 [R = Ph, Fe(C5H5)2] with the molybdenum complex Cp(CO)3Mo-Mo(CO)3Cp (Cp = cyclopentadienyl) in refluxing toluene resulted in the simple tetrahedral clusters Cp(CO)2Mo(P3N3F5)C-C(Ph)Mo(CO)2Cp (6) and Cp(CO)2Mo(P3N3F5)C-C(Fc)Mo(CO)2Cp (7) (Fc = ferrocenyl). A similar reaction of Cp(CO)3Mo-Mo(CO)3Cp with butadiyne-derived fluorophosphazenes, [(RC≡C-C≡C)(F)PN](PNF2)2 [R = Ph, Fe(C5H5)2], yielded the tetrahedral clusters Cp(CO)2Mo(P3N3F5)C-C(C≡CPh)Mo(CO)2Cp (8) and Cp(CO)2Mo(P3N3F5)C-C(C≡CFc)Mo(CO)2Cp (9) with the tetrahedral Mo2C2 unit forming exclusively with the alkyne unit of the butadiyne group bound to the cyclophosphazene ring. The crystal structures and infrared spectral data of these molybdenum clusters showed the presence of a semibridging carbonyl on one of the molybdenum units. All new compounds were characterized by IR, NMR [(1)H, (13)C{(1)H}, (31)P{(1)H}, and (19)F{(1)H}] and high-resolution mass spectrometry studies. Compounds 2, 3, 5, and 7-9 were also structurally characterized using single-crystal X-ray diffraction studies.

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Coordination and organometallic chemistry of cyclophosphazenes and polyphosphazenes

Chandrasekhar

Thomas

1993

Applied Organom Chemis

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The Reactions of Alkynlcyclophosphazenes with Metal Carbonyls

Cited by 14 publications

References 5 publications

Synthesis and Characterization of Novel Fluorophosphazene-Derived Cobaltacyclopentadienyl Metallacycles: Reagents for Assembly of Aryl-Bridged Fluorophosphazenes

Synthesis and Characterization of Novel Fluorophosphazene-Derived Cobaltacyclopentadienyl Metallacycles: Reagents for Assembly of Aryl-Bridged Fluorophosphazenes

Reactions of Alkyne- and Butadiyne-Derived Fluorinated Cyclophosphazenes with Diiron and Dimolybdenum Carbonyls

Coordination and organometallic chemistry of cyclophosphazenes and polyphosphazenes

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