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

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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.

Original languageEnglish
Pages (from-to)2798-2807
Number of pages10
JournalInorganic Chemistry
Volume26
Issue number17
DOIs
Publication statusPublished - 1987 Aug 1

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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