Diamond-shaped heterometallic complexes of iron(II) and copper(I) bridged by cyanide groups containing monodentate or bidentate phosphanes bound to copper(I), including an alternative structure based on the nature of the bidentate phosphane ligand

Donald J. Darensbourg, Way Zen Lee, M. Jason Adams, Jason C. Yarbrough

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22 Citations (Scopus)

Abstract

The diamond-shaped heterometallic cyanide-bridged complex of iron(II) and copper(I), [CpFe(CO)(μ-CN)2Cu(CH3CN)2]2 (1), has been synthesized from the reaction of K[CpFe(CO)(CN)2] and [Cu(CH3CN)4][BF4] in acetonitrile. Upon the addition of 2-4 equivalents of phosphane ligands to complex 1, the coordination geometry of the copper centers can be varied from trigonal planar as in [CpFe(CO)(μ-CN)2Cu(PCy3)]2 (2), to tetrahedral as found in [CpFe(CO)(μ-CN)2Cu(PCy3)2]2 (3). Analogous derivatives containing other phosphane ligands, namely PMe3, P(p-to-lyl)3, PMe2Ph, and PPh2Me have been synthesized as well. Prolonged exposure of complex 3 in CH2Cl2 to excess PCy3 has provided the bimetallic complex [CpFe(PCy3)(CN)(μ-CN)Cu(PCy3)2] (4), where the metal aggregate is disrupted and PCy3 has displaced CO at the iron center. Bidentate phosphane analogs of complex 3 have been prepared by adding two equivalents of dcpe [bis(dicyclohexylphosphanyl)-ethane] or dcpp [bis(dicyclohexylphosphanyl)propane] to complex 1. The solid-state structures of several of these diamond-shaped derivatives, in addition to complex 4, have been determined by X-ray crystallography. The overlapping diamond-shaped [Fe2(CN)4Cu2] cores, which form channels within the solids, are blocked by bulky, copper-bound phosphane ligands such as PCy3. However, in the case of the small phosphane PMe3, or the chelating phosphanes dcpe and dcpp, these channels are not blocked by the phosphane ligands; solvent molecules occupy the channels created by the overlapping metal cores instead. Alternatively, the complex [CpFe(CO)(CN)(μ-CN)Cu(dcpm)]2 (13), derived from bis(dicyclohexylphosphanyl)methane(dcpm), possesses two copper(I) centers, each in a distorted trigonal coordination geometry, bridged by two dcpm ligands to form an eight-membered metallacycle with a short CuI⋯CuI separation of 2.844 Å. The third ligand completing each copper's coordination sphere is a nitrogen-bound bridging cyanide group from a CpFe(CO)(CN)2 - anion.

Original languageEnglish
Pages (from-to)2811-2822
Number of pages12
JournalEuropean Journal of Inorganic Chemistry
Issue number11
DOIs
Publication statusPublished - 2001 Jan 1

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phosphine
Diamond
Cyanides
Carbon Monoxide
Copper
Iron
Ligands
Methane
Propane
Ethane
Metals
Derivatives
Geometry
X ray crystallography
Chelation
Anions

Keywords

  • Bridging ligands
  • Copper
  • Cyanides
  • Iron
  • P ligands

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

@article{6d014a19cfa642abb25ab9713e5b5356,
title = "Diamond-shaped heterometallic complexes of iron(II) and copper(I) bridged by cyanide groups containing monodentate or bidentate phosphanes bound to copper(I), including an alternative structure based on the nature of the bidentate phosphane ligand",
abstract = "The diamond-shaped heterometallic cyanide-bridged complex of iron(II) and copper(I), [CpFe(CO)(μ-CN)2Cu(CH3CN)2]2 (1), has been synthesized from the reaction of K[CpFe(CO)(CN)2] and [Cu(CH3CN)4][BF4] in acetonitrile. Upon the addition of 2-4 equivalents of phosphane ligands to complex 1, the coordination geometry of the copper centers can be varied from trigonal planar as in [CpFe(CO)(μ-CN)2Cu(PCy3)]2 (2), to tetrahedral as found in [CpFe(CO)(μ-CN)2Cu(PCy3)2]2 (3). Analogous derivatives containing other phosphane ligands, namely PMe3, P(p-to-lyl)3, PMe2Ph, and PPh2Me have been synthesized as well. Prolonged exposure of complex 3 in CH2Cl2 to excess PCy3 has provided the bimetallic complex [CpFe(PCy3)(CN)(μ-CN)Cu(PCy3)2] (4), where the metal aggregate is disrupted and PCy3 has displaced CO at the iron center. Bidentate phosphane analogs of complex 3 have been prepared by adding two equivalents of dcpe [bis(dicyclohexylphosphanyl)-ethane] or dcpp [bis(dicyclohexylphosphanyl)propane] to complex 1. The solid-state structures of several of these diamond-shaped derivatives, in addition to complex 4, have been determined by X-ray crystallography. The overlapping diamond-shaped [Fe2(CN)4Cu2] cores, which form channels within the solids, are blocked by bulky, copper-bound phosphane ligands such as PCy3. However, in the case of the small phosphane PMe3, or the chelating phosphanes dcpe and dcpp, these channels are not blocked by the phosphane ligands; solvent molecules occupy the channels created by the overlapping metal cores instead. Alternatively, the complex [CpFe(CO)(CN)(μ-CN)Cu(dcpm)]2 (13), derived from bis(dicyclohexylphosphanyl)methane(dcpm), possesses two copper(I) centers, each in a distorted trigonal coordination geometry, bridged by two dcpm ligands to form an eight-membered metallacycle with a short CuI⋯CuI separation of 2.844 {\AA}. The third ligand completing each copper's coordination sphere is a nitrogen-bound bridging cyanide group from a CpFe(CO)(CN)2 - anion.",
keywords = "Bridging ligands, Copper, Cyanides, Iron, P ligands",
author = "Darensbourg, {Donald J.} and Lee, {Way Zen} and Adams, {M. Jason} and Yarbrough, {Jason C.}",
year = "2001",
month = "1",
day = "1",
doi = "10.1002/1099-0682(200111)2001:11<2811::AID-EJIC2811>3.0.CO;2-A",
language = "English",
pages = "2811--2822",
journal = "Chemische Berichte",
issn = "0009-2940",
publisher = "Wiley-VCH Verlag",
number = "11",

}

TY - JOUR

T1 - Diamond-shaped heterometallic complexes of iron(II) and copper(I) bridged by cyanide groups containing monodentate or bidentate phosphanes bound to copper(I), including an alternative structure based on the nature of the bidentate phosphane ligand

AU - Darensbourg, Donald J.

AU - Lee, Way Zen

AU - Adams, M. Jason

AU - Yarbrough, Jason C.

PY - 2001/1/1

Y1 - 2001/1/1

N2 - The diamond-shaped heterometallic cyanide-bridged complex of iron(II) and copper(I), [CpFe(CO)(μ-CN)2Cu(CH3CN)2]2 (1), has been synthesized from the reaction of K[CpFe(CO)(CN)2] and [Cu(CH3CN)4][BF4] in acetonitrile. Upon the addition of 2-4 equivalents of phosphane ligands to complex 1, the coordination geometry of the copper centers can be varied from trigonal planar as in [CpFe(CO)(μ-CN)2Cu(PCy3)]2 (2), to tetrahedral as found in [CpFe(CO)(μ-CN)2Cu(PCy3)2]2 (3). Analogous derivatives containing other phosphane ligands, namely PMe3, P(p-to-lyl)3, PMe2Ph, and PPh2Me have been synthesized as well. Prolonged exposure of complex 3 in CH2Cl2 to excess PCy3 has provided the bimetallic complex [CpFe(PCy3)(CN)(μ-CN)Cu(PCy3)2] (4), where the metal aggregate is disrupted and PCy3 has displaced CO at the iron center. Bidentate phosphane analogs of complex 3 have been prepared by adding two equivalents of dcpe [bis(dicyclohexylphosphanyl)-ethane] or dcpp [bis(dicyclohexylphosphanyl)propane] to complex 1. The solid-state structures of several of these diamond-shaped derivatives, in addition to complex 4, have been determined by X-ray crystallography. The overlapping diamond-shaped [Fe2(CN)4Cu2] cores, which form channels within the solids, are blocked by bulky, copper-bound phosphane ligands such as PCy3. However, in the case of the small phosphane PMe3, or the chelating phosphanes dcpe and dcpp, these channels are not blocked by the phosphane ligands; solvent molecules occupy the channels created by the overlapping metal cores instead. Alternatively, the complex [CpFe(CO)(CN)(μ-CN)Cu(dcpm)]2 (13), derived from bis(dicyclohexylphosphanyl)methane(dcpm), possesses two copper(I) centers, each in a distorted trigonal coordination geometry, bridged by two dcpm ligands to form an eight-membered metallacycle with a short CuI⋯CuI separation of 2.844 Å. The third ligand completing each copper's coordination sphere is a nitrogen-bound bridging cyanide group from a CpFe(CO)(CN)2 - anion.

AB - The diamond-shaped heterometallic cyanide-bridged complex of iron(II) and copper(I), [CpFe(CO)(μ-CN)2Cu(CH3CN)2]2 (1), has been synthesized from the reaction of K[CpFe(CO)(CN)2] and [Cu(CH3CN)4][BF4] in acetonitrile. Upon the addition of 2-4 equivalents of phosphane ligands to complex 1, the coordination geometry of the copper centers can be varied from trigonal planar as in [CpFe(CO)(μ-CN)2Cu(PCy3)]2 (2), to tetrahedral as found in [CpFe(CO)(μ-CN)2Cu(PCy3)2]2 (3). Analogous derivatives containing other phosphane ligands, namely PMe3, P(p-to-lyl)3, PMe2Ph, and PPh2Me have been synthesized as well. Prolonged exposure of complex 3 in CH2Cl2 to excess PCy3 has provided the bimetallic complex [CpFe(PCy3)(CN)(μ-CN)Cu(PCy3)2] (4), where the metal aggregate is disrupted and PCy3 has displaced CO at the iron center. Bidentate phosphane analogs of complex 3 have been prepared by adding two equivalents of dcpe [bis(dicyclohexylphosphanyl)-ethane] or dcpp [bis(dicyclohexylphosphanyl)propane] to complex 1. The solid-state structures of several of these diamond-shaped derivatives, in addition to complex 4, have been determined by X-ray crystallography. The overlapping diamond-shaped [Fe2(CN)4Cu2] cores, which form channels within the solids, are blocked by bulky, copper-bound phosphane ligands such as PCy3. However, in the case of the small phosphane PMe3, or the chelating phosphanes dcpe and dcpp, these channels are not blocked by the phosphane ligands; solvent molecules occupy the channels created by the overlapping metal cores instead. Alternatively, the complex [CpFe(CO)(CN)(μ-CN)Cu(dcpm)]2 (13), derived from bis(dicyclohexylphosphanyl)methane(dcpm), possesses two copper(I) centers, each in a distorted trigonal coordination geometry, bridged by two dcpm ligands to form an eight-membered metallacycle with a short CuI⋯CuI separation of 2.844 Å. The third ligand completing each copper's coordination sphere is a nitrogen-bound bridging cyanide group from a CpFe(CO)(CN)2 - anion.

KW - Bridging ligands

KW - Copper

KW - Cyanides

KW - Iron

KW - P ligands

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