Synthesis and characterization of a monocyanide-bridged bimetallic iron(II) and copper(I) complex

D. J. Darensbourg; Way-Zen Lee; J. C. Yarbrough

doi:10.1021/ic010683z

Synthesis and characterization of a monocyanide-bridged bimetallic iron(II) and copper(I) complex

D. J. Darensbourg, Way-Zen Lee, J. C. Yarbrough

Department of Chemistry

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9 Citations (Scopus)

Abstract

The experiments reported here describe the interaction of the cyanide ligand in the neutral CpFe(CO)₂CN derivative with copper(I) in both acetonitrile and methylene chloride solutions. In acetonitrile solution, acetonitrile competes with the Fe-CN moiety for binding to copper(I), where an equilibrium is established with K_cq = 4.3 x 10³ ?? 25 °C. On the other hand, in methylene chloride, complete adduct formation is observed. Adduct formation in solution is based on shifts of the v_co and V_CN vibrations to higher frequencies, as compared to the corresponding values in CpFe(CO)₂CN, with v_cN being more significantly affected by complex formation. Upon adding 2 equiv of PCy₃ to a methylene chloride solution of CpFe(CO)₂CN and Cu(CH₃CN)₄⁺, the complex cation CpFe(CO)₂(μ-CN)Cu(PCy₃)₂⁺ is formed and isolated as its BF₄^- salt in crystalline form. X-ray crystallography has shown that the interatomic distances and angles in the parent complex CpFe(CO)₂CN and its copper(I) adduct are quite similar. Further, the Fe-CN-Cu bridge is nonlinear, displaying a C-N-Cu angle of 161.3(5)°.

Original language	English
Pages (from-to)	6533-6536
Number of pages	4
Journal	Inorganic Chemistry
Volume	40
Issue number	25
DOIs	https://doi.org/10.1021/ic010683z
Publication status	Published - 2001 Dec 3

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Synthesis and characterization of a monocyanide-bridged bimetallic iron(II) and copper(I) complex",

abstract = "The experiments reported here describe the interaction of the cyanide ligand in the neutral CpFe(CO)2CN derivative with copper(I) in both acetonitrile and methylene chloride solutions. In acetonitrile solution, acetonitrile competes with the Fe-CN moiety for binding to copper(I), where an equilibrium is established with Kcq = 4.3 x 103 ?? 25 °C. On the other hand, in methylene chloride, complete adduct formation is observed. Adduct formation in solution is based on shifts of the vco and VCN vibrations to higher frequencies, as compared to the corresponding values in CpFe(CO)2CN, with vcN being more significantly affected by complex formation. Upon adding 2 equiv of PCy3 to a methylene chloride solution of CpFe(CO)2CN and Cu(CH3CN)4+, the complex cation CpFe(CO)2(μ-CN)Cu(PCy3)2+ is formed and isolated as its BF4- salt in crystalline form. X-ray crystallography has shown that the interatomic distances and angles in the parent complex CpFe(CO)2CN and its copper(I) adduct are quite similar. Further, the Fe-CN-Cu bridge is nonlinear, displaying a C-N-Cu angle of 161.3(5)°.",

author = "Darensbourg, {D. J.} and Way-Zen Lee and Yarbrough, {J. C.}",

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AU - Darensbourg, D. J.

AU - Lee, Way-Zen

AU - Yarbrough, J. C.

PY - 2001/12/3

Y1 - 2001/12/3

N2 - The experiments reported here describe the interaction of the cyanide ligand in the neutral CpFe(CO)2CN derivative with copper(I) in both acetonitrile and methylene chloride solutions. In acetonitrile solution, acetonitrile competes with the Fe-CN moiety for binding to copper(I), where an equilibrium is established with Kcq = 4.3 x 103 ?? 25 °C. On the other hand, in methylene chloride, complete adduct formation is observed. Adduct formation in solution is based on shifts of the vco and VCN vibrations to higher frequencies, as compared to the corresponding values in CpFe(CO)2CN, with vcN being more significantly affected by complex formation. Upon adding 2 equiv of PCy3 to a methylene chloride solution of CpFe(CO)2CN and Cu(CH3CN)4+, the complex cation CpFe(CO)2(μ-CN)Cu(PCy3)2+ is formed and isolated as its BF4- salt in crystalline form. X-ray crystallography has shown that the interatomic distances and angles in the parent complex CpFe(CO)2CN and its copper(I) adduct are quite similar. Further, the Fe-CN-Cu bridge is nonlinear, displaying a C-N-Cu angle of 161.3(5)°.

AB - The experiments reported here describe the interaction of the cyanide ligand in the neutral CpFe(CO)2CN derivative with copper(I) in both acetonitrile and methylene chloride solutions. In acetonitrile solution, acetonitrile competes with the Fe-CN moiety for binding to copper(I), where an equilibrium is established with Kcq = 4.3 x 103 ?? 25 °C. On the other hand, in methylene chloride, complete adduct formation is observed. Adduct formation in solution is based on shifts of the vco and VCN vibrations to higher frequencies, as compared to the corresponding values in CpFe(CO)2CN, with vcN being more significantly affected by complex formation. Upon adding 2 equiv of PCy3 to a methylene chloride solution of CpFe(CO)2CN and Cu(CH3CN)4+, the complex cation CpFe(CO)2(μ-CN)Cu(PCy3)2+ is formed and isolated as its BF4- salt in crystalline form. X-ray crystallography has shown that the interatomic distances and angles in the parent complex CpFe(CO)2CN and its copper(I) adduct are quite similar. Further, the Fe-CN-Cu bridge is nonlinear, displaying a C-N-Cu angle of 161.3(5)°.

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Synthesis and characterization of a monocyanide-bridged bimetallic iron(II) and copper(I) complex

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