Transformations in the Bismuth-Iron Carbonyl Cluster System: Importance of Oxidation/Reduction Reactions. Crystal Structures of [Me4N]3[Bi2Fe4(CO)13]Cl and [Et4N][Bi2Fe2Co(CO)10]

Kenton H. Whitmire; Minghuey Shieh; Craig B. Lagrone; Brian H. Robinson; Ronald F. See; James C. Fettinger; Melvyn Rowen Churchill

doi:10.1021/ic00264a016

Transformations in the Bismuth-Iron Carbonyl Cluster System: Importance of Oxidation/Reduction Reactions. Crystal Structures of [Me₄N]₃[Bi₂Fe₄(CO)₁₃]Cl and [Et₄N][Bi₂Fe₂Co(CO)₁₀]

Kenton H. Whitmire^*, Minghuey Shieh, Craig B. Lagrone, Brian H. Robinson, Ronald F. See, James C. Fettinger, Melvyn Rowen Churchill

^*此作品的通信作者

研究成果: 雜誌貢獻 › 期刊論文 › 同行評審

36 引文斯高帕斯（Scopus）

摘要

The complex anion [Bi{Fe(CO)₄}₄]_3-reacts instantaneously with BiCl₃in CH₃CN to yield an unknown intermediate that is converted upon refluxing into a mixture of [BiFe₃(CO)₁₀]_-, [Bi₂Fe₄(CO)₁₃]_2-, and [Bi₄Fe₄(CO)₁₃]_2-. The cluster anion [Bi₂Fe₄(CO)₁₃]_2-, [1]_2-, isolated in 85% yield as the [Et₄N]₊salt from the reaction of Bi₂Fe₃(CO)₉with [Fe(CO)₄]_2-reacts with CO in CH₂C1₂to yield [Bi₄Fe₄(CO)₁₃]_2-and Fe(CO)₅. The [Et₄N]₊or Na₊salt of [l]_2-reacts with [Cu(CH₃CN)₄][BF₄] in CH₂C1₂to produce Bi₂Fe₃(CO)₉, Fe(CO)₅, and Fe₃(CO)₁₂. This methodology can be utilized to generate Bi₂Fe₃(CO)₉in high yield by using [Bi{Fe(CO)₄}₄]_3-as the starting material or in lower yields from the reaction of [BiFe₃(CO)₁₀]_-with [Cu(CH₃CN)₄] [BF₄]. Reaction of Bi₂Fe₃(CO)₉with [Co(CO)₄]_-yields the cluster anion [Bi₂Fe₂Co(CO)₁₀]_-, [2]_-, in which a Bi-Bi bond is formed with elimination of an iron vertex. The Bi₂Fe₃(CO)₉cluster is readily reduced electrochemically (E_1/2= -0.39 V) or chemically with Na/Hg, yielding sequentially [Bi₂Fe₃(CO)₉]_-and [Bi₂Fe₃(CO)₉]_2-. The complexes [Me₄N]₂[l].[Me₄N]Cl and [Et₄N][2] have been characterized by X-ray crystallography. The former cocrystallizes with one molecule of [Me₄N]Cl in the centrosymmetric triclinic space group PI with a = 12.642 (3) A, b = 13.215 (3) A, c = 13.589 (5) A, a = 87.343 (27)°, β = 71.132 (24)°, y = 75.592 (20)°, V = 2079.3 (11) A₃, and Z = 2. The structure was refined to R_F= 6.1% for all 5467 reflections (R_F= 4.4% for those 4226 reflections with| F₀| > 6.0σ(|F_o|)). The nucleus of the dianion consists of a square-pyramidal Bi₂Fe₃cluster (with an apical Fe and trans Bi atoms) with an additional Fe atom bonded to a Bi atom; the pendant Fe atom is linked to four terminal carbonyl ligands, while the other three Fe atoms each bear three such ligands. Intermetallic distances are as follows: Bi.Bi = 3.398 (1), Bi-Fe = 2.592 (2)-2.687 (2), and Fe-Fe = 2.796 (2)-2.808 (2) A. The compound [Et₄N] [2] crystallizes in the centrosymmetric triclinic space group Pi with a = 10.205 (4) A, b = 11.250 (8) A, c = 13.125 (6) A, a = 70.30 (5)°, β = 76.94 (3)°, γ = 76.89 (5)°, V = 1363.1 (14) A₃, and Z = 2. Diffraction data (Mo Ka, 2θ = 4-45°) were collected on a Syntex P2₁four-circle diffractometer, and the structure was refined to R_F= 8.3% for 2492 reflections with| F₀| > 3σ(|F₀|) (R_F= 6.4% for those 1998 reflections with| F₀| > 6σ(|F₀|)). The anionic nucleus consists of a tetrahedral Bi₂Fe₂cluster in which a Co atom bridges the Bi-Bi bond; each Fe atom bears three terminal carbonyl ligands, while the Co is associated with four. Intermetallic distances are as follows: Bi-Bi = 3.092 (2), Bi-Fe = 2.669 (5)-2.693 (5), Bi-Co = 2.868 (5)-2.894 (5), and Fe-Fe = 2.682 (7) A.

原文	英語
頁（從 - 到）	2798-2807
頁數	10
期刊	Inorganic Chemistry
卷	26
發行號	17
DOIs	https://doi.org/10.1021/ic00264a016
出版狀態	已發佈 - 1987 8月 1
對外發佈	是

ASJC Scopus subject areas

物理與理論化學
無機化學

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10.1021/ic00264a016

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Whitmire, K. H., Shieh, M., Lagrone, C. B., Robinson, B. H., See, R. F., Fettinger, J. C., & Churchill, M. R. (1987). Transformations in the Bismuth-Iron Carbonyl Cluster System: Importance of Oxidation/Reduction Reactions. Crystal Structures of [Me₄N]₃[Bi₂Fe₄(CO)₁₃]Cl and [Et₄N][Bi₂Fe₂Co(CO)₁₀]. Inorganic Chemistry, 26(17), 2798-2807. https://doi.org/10.1021/ic00264a016

Transformations in the Bismuth-Iron Carbonyl Cluster System: Importance of Oxidation/Reduction Reactions. Crystal Structures of [Me₄N]₃[Bi₂Fe₄(CO)₁₃]Cl and [Et₄N][Bi₂Fe₂Co(CO)₁₀]. / Whitmire, Kenton H.; Shieh, Minghuey; Lagrone, Craig B. 等.
於: Inorganic Chemistry, 卷 26, 編號 17, 01.08.1987, p. 2798-2807.

研究成果: 雜誌貢獻 › 期刊論文 › 同行評審

@article{915de53be58a4caebdcbabfe15602174,

title = "Transformations in the Bismuth-Iron Carbonyl Cluster System: Importance of Oxidation/Reduction Reactions. Crystal Structures of [Me4N]3[Bi2Fe4(CO)13]Cl and [Et4N][Bi2Fe2Co(CO)10]",

abstract = "The complex anion [Bi{Fe(CO)4}4]3-reacts instantaneously with BiCl3in CH3CN to yield an unknown intermediate that is converted upon refluxing into a mixture of [BiFe3(CO)10]-, [Bi2Fe4(CO)13]2-, and [Bi4Fe4(CO)13]2-. The cluster anion [Bi2Fe4(CO)13]2-, [1]2-, isolated in 85% yield as the [Et4N]+salt from the reaction of Bi2Fe3(CO)9with [Fe(CO)4]2-reacts with CO in CH2C12to yield [Bi4Fe4(CO)13]2-and Fe(CO)5. The [Et4N]+or Na+salt of [l]2-reacts with [Cu(CH3CN)4][BF4] in CH2C12to produce Bi2Fe3(CO)9, Fe(CO)5, and Fe3(CO)12. This methodology can be utilized to generate Bi2Fe3(CO)9in high yield by using [Bi{Fe(CO)4}4]3-as the starting material or in lower yields from the reaction of [BiFe3(CO)10]-with [Cu(CH3CN)4] [BF4]. Reaction of Bi2Fe3(CO)9with [Co(CO)4]-yields the cluster anion [Bi2Fe2Co(CO)10]-, [2]-, in which a Bi-Bi bond is formed with elimination of an iron vertex. The Bi2Fe3(CO)9cluster is readily reduced electrochemically (E1/2= -0.39 V) or chemically with Na/Hg, yielding sequentially [Bi2Fe3(CO)9]-and [Bi2Fe3(CO)9]2-. The complexes [Me4N]2[l].[Me4N]Cl and [Et4N][2] have been characterized by X-ray crystallography. The former cocrystallizes with one molecule of [Me4N]Cl in the centrosymmetric triclinic space group PI with a = 12.642 (3) A, b = 13.215 (3) A, c = 13.589 (5) A, a = 87.343 (27)°, β = 71.132 (24)°, y = 75.592 (20)°, V = 2079.3 (11) A3, and Z = 2. The structure was refined to RF= 6.1% for all 5467 reflections (RF= 4.4% for those 4226 reflections with| F0| > 6.0σ(|Fo|)). The nucleus of the dianion consists of a square-pyramidal Bi2Fe3cluster (with an apical Fe and trans Bi atoms) with an additional Fe atom bonded to a Bi atom; the pendant Fe atom is linked to four terminal carbonyl ligands, while the other three Fe atoms each bear three such ligands. Intermetallic distances are as follows: Bi.Bi = 3.398 (1), Bi-Fe = 2.592 (2)-2.687 (2), and Fe-Fe = 2.796 (2)-2.808 (2) A. The compound [Et4N] [2] crystallizes in the centrosymmetric triclinic space group Pi with a = 10.205 (4) A, b = 11.250 (8) A, c = 13.125 (6) A, a = 70.30 (5)°, β = 76.94 (3)°, γ = 76.89 (5)°, V = 1363.1 (14) A3, and Z = 2. Diffraction data (Mo Ka, 2θ = 4-45°) were collected on a Syntex P21four-circle diffractometer, and the structure was refined to RF= 8.3% for 2492 reflections with| F0| > 3σ(|F0|) (RF= 6.4% for those 1998 reflections with| F0| > 6σ(|F0|)). The anionic nucleus consists of a tetrahedral Bi2Fe2cluster in which a Co atom bridges the Bi-Bi bond; each Fe atom bears three terminal carbonyl ligands, while the Co is associated with four. Intermetallic distances are as follows: Bi-Bi = 3.092 (2), Bi-Fe = 2.669 (5)-2.693 (5), Bi-Co = 2.868 (5)-2.894 (5), and Fe-Fe = 2.682 (7) A.",

author = "Whitmire, {Kenton H.} and Minghuey Shieh and Lagrone, {Craig B.} and Robinson, {Brian H.} and See, {Ronald F.} and Fettinger, {James C.} and Churchill, {Melvyn Rowen}",

year = "1987",

month = aug,

day = "1",

doi = "10.1021/ic00264a016",

language = "English",

volume = "26",

pages = "2798--2807",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "17",

}

TY - JOUR

T1 - Transformations in the Bismuth-Iron Carbonyl Cluster System

T2 - Importance of Oxidation/Reduction Reactions. Crystal Structures of [Me4N]3[Bi2Fe4(CO)13]Cl and [Et4N][Bi2Fe2Co(CO)10]

AU - Whitmire, Kenton H.

AU - Shieh, Minghuey

AU - Lagrone, Craig B.

AU - Robinson, Brian H.

AU - See, Ronald F.

AU - Fettinger, James C.

AU - Churchill, Melvyn Rowen

PY - 1987/8/1

Y1 - 1987/8/1

N2 - The complex anion [Bi{Fe(CO)4}4]3-reacts instantaneously with BiCl3in CH3CN to yield an unknown intermediate that is converted upon refluxing into a mixture of [BiFe3(CO)10]-, [Bi2Fe4(CO)13]2-, and [Bi4Fe4(CO)13]2-. The cluster anion [Bi2Fe4(CO)13]2-, [1]2-, isolated in 85% yield as the [Et4N]+salt from the reaction of Bi2Fe3(CO)9with [Fe(CO)4]2-reacts with CO in CH2C12to yield [Bi4Fe4(CO)13]2-and Fe(CO)5. The [Et4N]+or Na+salt of [l]2-reacts with [Cu(CH3CN)4][BF4] in CH2C12to produce Bi2Fe3(CO)9, Fe(CO)5, and Fe3(CO)12. This methodology can be utilized to generate Bi2Fe3(CO)9in high yield by using [Bi{Fe(CO)4}4]3-as the starting material or in lower yields from the reaction of [BiFe3(CO)10]-with [Cu(CH3CN)4] [BF4]. Reaction of Bi2Fe3(CO)9with [Co(CO)4]-yields the cluster anion [Bi2Fe2Co(CO)10]-, [2]-, in which a Bi-Bi bond is formed with elimination of an iron vertex. The Bi2Fe3(CO)9cluster is readily reduced electrochemically (E1/2= -0.39 V) or chemically with Na/Hg, yielding sequentially [Bi2Fe3(CO)9]-and [Bi2Fe3(CO)9]2-. The complexes [Me4N]2[l].[Me4N]Cl and [Et4N][2] have been characterized by X-ray crystallography. The former cocrystallizes with one molecule of [Me4N]Cl in the centrosymmetric triclinic space group PI with a = 12.642 (3) A, b = 13.215 (3) A, c = 13.589 (5) A, a = 87.343 (27)°, β = 71.132 (24)°, y = 75.592 (20)°, V = 2079.3 (11) A3, and Z = 2. The structure was refined to RF= 6.1% for all 5467 reflections (RF= 4.4% for those 4226 reflections with| F0| > 6.0σ(|Fo|)). The nucleus of the dianion consists of a square-pyramidal Bi2Fe3cluster (with an apical Fe and trans Bi atoms) with an additional Fe atom bonded to a Bi atom; the pendant Fe atom is linked to four terminal carbonyl ligands, while the other three Fe atoms each bear three such ligands. Intermetallic distances are as follows: Bi.Bi = 3.398 (1), Bi-Fe = 2.592 (2)-2.687 (2), and Fe-Fe = 2.796 (2)-2.808 (2) A. The compound [Et4N] [2] crystallizes in the centrosymmetric triclinic space group Pi with a = 10.205 (4) A, b = 11.250 (8) A, c = 13.125 (6) A, a = 70.30 (5)°, β = 76.94 (3)°, γ = 76.89 (5)°, V = 1363.1 (14) A3, and Z = 2. Diffraction data (Mo Ka, 2θ = 4-45°) were collected on a Syntex P21four-circle diffractometer, and the structure was refined to RF= 8.3% for 2492 reflections with| F0| > 3σ(|F0|) (RF= 6.4% for those 1998 reflections with| F0| > 6σ(|F0|)). The anionic nucleus consists of a tetrahedral Bi2Fe2cluster in which a Co atom bridges the Bi-Bi bond; each Fe atom bears three terminal carbonyl ligands, while the Co is associated with four. Intermetallic distances are as follows: Bi-Bi = 3.092 (2), Bi-Fe = 2.669 (5)-2.693 (5), Bi-Co = 2.868 (5)-2.894 (5), and Fe-Fe = 2.682 (7) A.

AB - The complex anion [Bi{Fe(CO)4}4]3-reacts instantaneously with BiCl3in CH3CN to yield an unknown intermediate that is converted upon refluxing into a mixture of [BiFe3(CO)10]-, [Bi2Fe4(CO)13]2-, and [Bi4Fe4(CO)13]2-. The cluster anion [Bi2Fe4(CO)13]2-, [1]2-, isolated in 85% yield as the [Et4N]+salt from the reaction of Bi2Fe3(CO)9with [Fe(CO)4]2-reacts with CO in CH2C12to yield [Bi4Fe4(CO)13]2-and Fe(CO)5. The [Et4N]+or Na+salt of [l]2-reacts with [Cu(CH3CN)4][BF4] in CH2C12to produce Bi2Fe3(CO)9, Fe(CO)5, and Fe3(CO)12. This methodology can be utilized to generate Bi2Fe3(CO)9in high yield by using [Bi{Fe(CO)4}4]3-as the starting material or in lower yields from the reaction of [BiFe3(CO)10]-with [Cu(CH3CN)4] [BF4]. Reaction of Bi2Fe3(CO)9with [Co(CO)4]-yields the cluster anion [Bi2Fe2Co(CO)10]-, [2]-, in which a Bi-Bi bond is formed with elimination of an iron vertex. The Bi2Fe3(CO)9cluster is readily reduced electrochemically (E1/2= -0.39 V) or chemically with Na/Hg, yielding sequentially [Bi2Fe3(CO)9]-and [Bi2Fe3(CO)9]2-. The complexes [Me4N]2[l].[Me4N]Cl and [Et4N][2] have been characterized by X-ray crystallography. The former cocrystallizes with one molecule of [Me4N]Cl in the centrosymmetric triclinic space group PI with a = 12.642 (3) A, b = 13.215 (3) A, c = 13.589 (5) A, a = 87.343 (27)°, β = 71.132 (24)°, y = 75.592 (20)°, V = 2079.3 (11) A3, and Z = 2. The structure was refined to RF= 6.1% for all 5467 reflections (RF= 4.4% for those 4226 reflections with| F0| > 6.0σ(|Fo|)). The nucleus of the dianion consists of a square-pyramidal Bi2Fe3cluster (with an apical Fe and trans Bi atoms) with an additional Fe atom bonded to a Bi atom; the pendant Fe atom is linked to four terminal carbonyl ligands, while the other three Fe atoms each bear three such ligands. Intermetallic distances are as follows: Bi.Bi = 3.398 (1), Bi-Fe = 2.592 (2)-2.687 (2), and Fe-Fe = 2.796 (2)-2.808 (2) A. The compound [Et4N] [2] crystallizes in the centrosymmetric triclinic space group Pi with a = 10.205 (4) A, b = 11.250 (8) A, c = 13.125 (6) A, a = 70.30 (5)°, β = 76.94 (3)°, γ = 76.89 (5)°, V = 1363.1 (14) A3, and Z = 2. Diffraction data (Mo Ka, 2θ = 4-45°) were collected on a Syntex P21four-circle diffractometer, and the structure was refined to RF= 8.3% for 2492 reflections with| F0| > 3σ(|F0|) (RF= 6.4% for those 1998 reflections with| F0| > 6σ(|F0|)). The anionic nucleus consists of a tetrahedral Bi2Fe2cluster in which a Co atom bridges the Bi-Bi bond; each Fe atom bears three terminal carbonyl ligands, while the Co is associated with four. Intermetallic distances are as follows: Bi-Bi = 3.092 (2), Bi-Fe = 2.669 (5)-2.693 (5), Bi-Co = 2.868 (5)-2.894 (5), and Fe-Fe = 2.682 (7) A.

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Transformations in the Bismuth-Iron Carbonyl Cluster System: Importance of Oxidation/Reduction Reactions. Crystal Structures of [Me4N]3[Bi2Fe4(CO)13]Cl and [Et4N][Bi2Fe2Co(CO)10]

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Transformations in the Bismuth-Iron Carbonyl Cluster System: Importance of Oxidation/Reduction Reactions. Crystal Structures of [Me₄N]₃[Bi₂Fe₄(CO)₁₃]Cl and [Et₄N][Bi₂Fe₂Co(CO)₁₀]