Synthesis and Reactivity of an Anionic Tetrairon Nitrido Cluster. Crystal and Molecular Structure of PPN[Fe4N(CO)12]

Douglas E. Fjare; Wayne L Gladfelter

doi:10.1021/ic50224a075

Synthesis and Reactivity of an Anionic Tetrairon Nitrido Cluster. Crystal and Molecular Structure of PPN[Fe₄N(CO)₁₂]

Douglas E. Fjare, Wayne L Gladfelter

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

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Abstract

The reaction of PPN[Fe(CO)₃(NO)] (PPN = bis(triphenylphosphin)iminium cation) with Fe₃(CO)₁₂ produces the nitrido cluster PPN[Fe_4N(CO)₁₂]. The structure was determined by single-crystal X-ray crystallography [PI space group, Z = 2, a = 10.700 (2)Å, b = 14.146 (3)Å, c = 16.249 (3)Å, α = 91.15 (1)°, β = 94.55 (2)°, γ = 97.52 (2)°] and found to contain a butterfly arrangement of iron atoms with the nitrogen situated in the center of the cluster. [Fe₄N(CO)₁₂]^- reacts with acids giving several products, of which Fe₄N(CO)₁₂H is the major derivative. The remaining products, apparently formed when excess acid and free carbon monoxide are present, are Fe₄N(CO)₁₁(NO), Fe₃(NH)(CO)₁₀, and Fe₃(NH)₂(CO)₉. The last two imido clusters have been characterized by comparison to existing related compounds. The structure of Fe₄N(CO)₁₁(NO) likely contains the same Fe₄N moiety as [Fe₄N(CO)₁₂]^-, although other structures are possible. The reaction of NOPF₆ with PPN[Fe₄N(CO)₁₂] produces Fe₄N(CO)₁₁(NO) in 62% yield.

Original language	English (US)
Pages (from-to)	3533-3539
Number of pages	7
Journal	Inorganic chemistry
Volume	20
Issue number	10
DOIs	https://doi.org/10.1021/ic50224a075
State	Published - Oct 1981

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@article{eaa35017233044e2bbb1767cb8c0e5c5,

title = "Synthesis and Reactivity of an Anionic Tetrairon Nitrido Cluster. Crystal and Molecular Structure of PPN[Fe4N(CO)12]",

abstract = "The reaction of PPN[Fe(CO)3(NO)] (PPN = bis(triphenylphosphin)iminium cation) with Fe3(CO)12 produces the nitrido cluster PPN[Fe4N(CO)12]. The structure was determined by single-crystal X-ray crystallography [PI space group, Z = 2, a = 10.700 (2){\AA}, b = 14.146 (3){\AA}, c = 16.249 (3){\AA}, α = 91.15 (1)°, β = 94.55 (2)°, γ = 97.52 (2)°] and found to contain a butterfly arrangement of iron atoms with the nitrogen situated in the center of the cluster. [Fe4N(CO)12]- reacts with acids giving several products, of which Fe4N(CO)12H is the major derivative. The remaining products, apparently formed when excess acid and free carbon monoxide are present, are Fe4N(CO)11(NO), Fe3(NH)(CO)10, and Fe3(NH)2(CO)9. The last two imido clusters have been characterized by comparison to existing related compounds. The structure of Fe4N(CO)11(NO) likely contains the same Fe4N moiety as [Fe4N(CO)12]-, although other structures are possible. The reaction of NOPF6 with PPN[Fe4N(CO)12] produces Fe4N(CO)11(NO) in 62% yield.",

author = "Fjare, {Douglas E.} and Gladfelter, {Wayne L}",

year = "1981",

month = oct,

doi = "10.1021/ic50224a075",

language = "English (US)",

volume = "20",

pages = "3533--3539",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "10",

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T1 - Synthesis and Reactivity of an Anionic Tetrairon Nitrido Cluster. Crystal and Molecular Structure of PPN[Fe4N(CO)12]

AU - Fjare, Douglas E.

AU - Gladfelter, Wayne L

PY - 1981/10

Y1 - 1981/10

N2 - The reaction of PPN[Fe(CO)3(NO)] (PPN = bis(triphenylphosphin)iminium cation) with Fe3(CO)12 produces the nitrido cluster PPN[Fe4N(CO)12]. The structure was determined by single-crystal X-ray crystallography [PI space group, Z = 2, a = 10.700 (2)Å, b = 14.146 (3)Å, c = 16.249 (3)Å, α = 91.15 (1)°, β = 94.55 (2)°, γ = 97.52 (2)°] and found to contain a butterfly arrangement of iron atoms with the nitrogen situated in the center of the cluster. [Fe4N(CO)12]- reacts with acids giving several products, of which Fe4N(CO)12H is the major derivative. The remaining products, apparently formed when excess acid and free carbon monoxide are present, are Fe4N(CO)11(NO), Fe3(NH)(CO)10, and Fe3(NH)2(CO)9. The last two imido clusters have been characterized by comparison to existing related compounds. The structure of Fe4N(CO)11(NO) likely contains the same Fe4N moiety as [Fe4N(CO)12]-, although other structures are possible. The reaction of NOPF6 with PPN[Fe4N(CO)12] produces Fe4N(CO)11(NO) in 62% yield.

AB - The reaction of PPN[Fe(CO)3(NO)] (PPN = bis(triphenylphosphin)iminium cation) with Fe3(CO)12 produces the nitrido cluster PPN[Fe4N(CO)12]. The structure was determined by single-crystal X-ray crystallography [PI space group, Z = 2, a = 10.700 (2)Å, b = 14.146 (3)Å, c = 16.249 (3)Å, α = 91.15 (1)°, β = 94.55 (2)°, γ = 97.52 (2)°] and found to contain a butterfly arrangement of iron atoms with the nitrogen situated in the center of the cluster. [Fe4N(CO)12]- reacts with acids giving several products, of which Fe4N(CO)12H is the major derivative. The remaining products, apparently formed when excess acid and free carbon monoxide are present, are Fe4N(CO)11(NO), Fe3(NH)(CO)10, and Fe3(NH)2(CO)9. The last two imido clusters have been characterized by comparison to existing related compounds. The structure of Fe4N(CO)11(NO) likely contains the same Fe4N moiety as [Fe4N(CO)12]-, although other structures are possible. The reaction of NOPF6 with PPN[Fe4N(CO)12] produces Fe4N(CO)11(NO) in 62% yield.

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Synthesis and Reactivity of an Anionic Tetrairon Nitrido Cluster. Crystal and Molecular Structure of PPN[Fe₄N(CO)₁₂]

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