Metal-metal bond cleavage reactions. The crystallization and solid state structural characterization of cadmium tetracarbonyliron, CdFe(CO)4

Richard D. Ernst, Tobin J Marks, James A. Ibers

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Abstract

The classical metal-metal bonded oligomer CdFe(CO)4 (but not the isomorphous HgFe(CO)4) can be completely cleaved by certain Lewis bases (B) to yield species of the formulation BnCdFe(CO)4, n = 2 or 3. Reversal of the cleavage allows, for the first time, crystallization of CdFe(CO)4 and determination of its molecular structure by single-crystal x-ray diffraction. The compound crystallizes from acetone-water in the monoclinic space group C2h5-P21/n, with two tetrameric [CdFe(CO)4]4 units and four molecules of acetone in a unit cell of dimensions a = 6.292 (4), b = 10.566 (6), c = 26.024 (11) Å, β = 97.80(3)°. Full-matrix least-squares refinement gave a final value of the conventional R index (on F) of 0.032 for 1602 reflections having Fo2 > 3σ(Fo2). The molecular structure consists of a nearly planar, centrosymmetric, eight-membered ring of alternating Cd and cis-Fe(CO)4 units. The geometry deviates from D4h square symmetry principally in that two opposite Fe-Cd-Fe angles are 170.25 (5)° and two are 189.85 (5)°. This reflects weak coordination of two cadmium atoms to acetone oxygen atoms (Cd-O = 2.688 (9) Å). The Cd-Fe distances are within experimental error all equal at 2.562 (3) Å. The major distortion from octahedral symmetry about the Fe(CO)4 groups is a bending of the axial carbonyl ligands toward the ring centroid and away from the vector perpendicular to the plane containing the metal atoms. The result is an average C-Fe-C angle of 154.7 (4)° for these groups. The acetone can be removed from the structure with minimal changes in the metal-metal bonding geometry. The base-induced cleavage reaction for this group II system is similar to the previously reported cleavage of [R2MFe(CO)4]2 molecules where M = Ge, Sn, Pb.

Original languageEnglish
Pages (from-to)2090-2098
Number of pages9
JournalJournal of the American Chemical Society
Volume99
Issue number7
Publication statusPublished - 1977

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Carbon Monoxide
Crystallization
Cadmium
Acetone
Metals
Atoms
Molecular structure
Molecular Structure
Molecules
Geometry
Oligomers
Lewis Bases
Diffraction
Ligands
Single crystals
X rays
Least-Squares Analysis
Oxygen
X-Rays
Water

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

@article{acd7924334df40fe856b593d80cb2cb4,
title = "Metal-metal bond cleavage reactions. The crystallization and solid state structural characterization of cadmium tetracarbonyliron, CdFe(CO)4",
abstract = "The classical metal-metal bonded oligomer CdFe(CO)4 (but not the isomorphous HgFe(CO)4) can be completely cleaved by certain Lewis bases (B) to yield species of the formulation BnCdFe(CO)4, n = 2 or 3. Reversal of the cleavage allows, for the first time, crystallization of CdFe(CO)4 and determination of its molecular structure by single-crystal x-ray diffraction. The compound crystallizes from acetone-water in the monoclinic space group C2h5-P21/n, with two tetrameric [CdFe(CO)4]4 units and four molecules of acetone in a unit cell of dimensions a = 6.292 (4), b = 10.566 (6), c = 26.024 (11) {\AA}, β = 97.80(3)°. Full-matrix least-squares refinement gave a final value of the conventional R index (on F) of 0.032 for 1602 reflections having Fo2 > 3σ(Fo2). The molecular structure consists of a nearly planar, centrosymmetric, eight-membered ring of alternating Cd and cis-Fe(CO)4 units. The geometry deviates from D4h square symmetry principally in that two opposite Fe-Cd-Fe angles are 170.25 (5)° and two are 189.85 (5)°. This reflects weak coordination of two cadmium atoms to acetone oxygen atoms (Cd-O = 2.688 (9) {\AA}). The Cd-Fe distances are within experimental error all equal at 2.562 (3) {\AA}. The major distortion from octahedral symmetry about the Fe(CO)4 groups is a bending of the axial carbonyl ligands toward the ring centroid and away from the vector perpendicular to the plane containing the metal atoms. The result is an average C-Fe-C angle of 154.7 (4)° for these groups. The acetone can be removed from the structure with minimal changes in the metal-metal bonding geometry. The base-induced cleavage reaction for this group II system is similar to the previously reported cleavage of [R2MFe(CO)4]2 molecules where M = Ge, Sn, Pb.",
author = "Ernst, {Richard D.} and Marks, {Tobin J} and Ibers, {James A.}",
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journal = "Journal of the American Chemical Society",
issn = "0002-7863",
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T1 - Metal-metal bond cleavage reactions. The crystallization and solid state structural characterization of cadmium tetracarbonyliron, CdFe(CO)4

AU - Ernst, Richard D.

AU - Marks, Tobin J

AU - Ibers, James A.

PY - 1977

Y1 - 1977

N2 - The classical metal-metal bonded oligomer CdFe(CO)4 (but not the isomorphous HgFe(CO)4) can be completely cleaved by certain Lewis bases (B) to yield species of the formulation BnCdFe(CO)4, n = 2 or 3. Reversal of the cleavage allows, for the first time, crystallization of CdFe(CO)4 and determination of its molecular structure by single-crystal x-ray diffraction. The compound crystallizes from acetone-water in the monoclinic space group C2h5-P21/n, with two tetrameric [CdFe(CO)4]4 units and four molecules of acetone in a unit cell of dimensions a = 6.292 (4), b = 10.566 (6), c = 26.024 (11) Å, β = 97.80(3)°. Full-matrix least-squares refinement gave a final value of the conventional R index (on F) of 0.032 for 1602 reflections having Fo2 > 3σ(Fo2). The molecular structure consists of a nearly planar, centrosymmetric, eight-membered ring of alternating Cd and cis-Fe(CO)4 units. The geometry deviates from D4h square symmetry principally in that two opposite Fe-Cd-Fe angles are 170.25 (5)° and two are 189.85 (5)°. This reflects weak coordination of two cadmium atoms to acetone oxygen atoms (Cd-O = 2.688 (9) Å). The Cd-Fe distances are within experimental error all equal at 2.562 (3) Å. The major distortion from octahedral symmetry about the Fe(CO)4 groups is a bending of the axial carbonyl ligands toward the ring centroid and away from the vector perpendicular to the plane containing the metal atoms. The result is an average C-Fe-C angle of 154.7 (4)° for these groups. The acetone can be removed from the structure with minimal changes in the metal-metal bonding geometry. The base-induced cleavage reaction for this group II system is similar to the previously reported cleavage of [R2MFe(CO)4]2 molecules where M = Ge, Sn, Pb.

AB - The classical metal-metal bonded oligomer CdFe(CO)4 (but not the isomorphous HgFe(CO)4) can be completely cleaved by certain Lewis bases (B) to yield species of the formulation BnCdFe(CO)4, n = 2 or 3. Reversal of the cleavage allows, for the first time, crystallization of CdFe(CO)4 and determination of its molecular structure by single-crystal x-ray diffraction. The compound crystallizes from acetone-water in the monoclinic space group C2h5-P21/n, with two tetrameric [CdFe(CO)4]4 units and four molecules of acetone in a unit cell of dimensions a = 6.292 (4), b = 10.566 (6), c = 26.024 (11) Å, β = 97.80(3)°. Full-matrix least-squares refinement gave a final value of the conventional R index (on F) of 0.032 for 1602 reflections having Fo2 > 3σ(Fo2). The molecular structure consists of a nearly planar, centrosymmetric, eight-membered ring of alternating Cd and cis-Fe(CO)4 units. The geometry deviates from D4h square symmetry principally in that two opposite Fe-Cd-Fe angles are 170.25 (5)° and two are 189.85 (5)°. This reflects weak coordination of two cadmium atoms to acetone oxygen atoms (Cd-O = 2.688 (9) Å). The Cd-Fe distances are within experimental error all equal at 2.562 (3) Å. The major distortion from octahedral symmetry about the Fe(CO)4 groups is a bending of the axial carbonyl ligands toward the ring centroid and away from the vector perpendicular to the plane containing the metal atoms. The result is an average C-Fe-C angle of 154.7 (4)° for these groups. The acetone can be removed from the structure with minimal changes in the metal-metal bonding geometry. The base-induced cleavage reaction for this group II system is similar to the previously reported cleavage of [R2MFe(CO)4]2 molecules where M = Ge, Sn, Pb.

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