Metal-metal bond cleavage reactions. The crystal and molecular structure of (2,2′-bipyridyl)cadmium tetracarbonyliron, (bpy)CdFe(CO)4

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

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Abstract

The complex (bpy)CdFe(CO)4 crystallizes from hot 1,2,4-trichlorobenzene as a trimer with the stoichiometry [(bpy)CdFe(CO)4]3·3/4C6H 3Cl3. The crystals belong to the tetragonal space group S41-P4 with eight six-membered metal-metal bonded rings and six solvent molecules in a unit cell of dimensions a = b = 29.049 (10), c = 13.241 (5) Å, V = 11 170 Å3. Full-matrix least-squares refinement yielded a final value of the conventional R index (on F) of 0.066 for 5643 reflections having Fo2 > 3σ(Fo2). The molecular structure consists of nearly planar rings of alternating cis-Fe(CO)4 and (bpy)Cd units. The ring is distorted from ideal D3h to approximate C2 symmetry by compression along a C2 axis in the plane of the ring. All Fe-Cd distances are equal within experimental error [2.640 (7) Å]. The Cd-Fe-Cd angles vary from 138.81 (15) to 148.40 (15)°, and the Fe-Cd-Fe angles from 94.78 (14) to 102.04 (16)°. The iron coordination geometry is significantly distorted from an octahedral one toward a tetrahedral one in which cadmium atoms cap two of the faces. There is evidence for a weak semibridging interaction between carbonyl carbon and cadmium atoms. The Cd-Fe bonding in [(bpy)CdFe(CO)4]3 appears to be more ionic than in [CdFe(CO)4]4. The trimeric compound dissociates in benzene solution.

Original languageEnglish
Pages (from-to)2098-2107
Number of pages10
JournalJournal of the American Chemical Society
Volume99
Issue number7
Publication statusPublished - 1977

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2,2'-Dipyridyl
Chemical bonds
Carbon Monoxide
Molecular Structure
Cadmium
Molecular structure
Crystal structure
Metals
Atoms
Stoichiometry
Benzene
Iron
Crystals
Molecules
Carbon
Geometry
Least-Squares Analysis

ASJC Scopus subject areas

  • Chemistry(all)

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Metal-metal bond cleavage reactions. The crystal and molecular structure of (2,2′-bipyridyl)cadmium tetracarbonyliron, (bpy)CdFe(CO)4. / Ernst, Richard D.; Marks, Tobin J; Ibers, James A.

In: Journal of the American Chemical Society, Vol. 99, No. 7, 1977, p. 2098-2107.

Research output: Contribution to journalArticle

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abstract = "The complex (bpy)CdFe(CO)4 crystallizes from hot 1,2,4-trichlorobenzene as a trimer with the stoichiometry [(bpy)CdFe(CO)4]3·3/4C6H 3Cl3. The crystals belong to the tetragonal space group S41-P4 with eight six-membered metal-metal bonded rings and six solvent molecules in a unit cell of dimensions a = b = 29.049 (10), c = 13.241 (5) {\AA}, V = 11 170 {\AA}3. Full-matrix least-squares refinement yielded a final value of the conventional R index (on F) of 0.066 for 5643 reflections having Fo2 > 3σ(Fo2). The molecular structure consists of nearly planar rings of alternating cis-Fe(CO)4 and (bpy)Cd units. The ring is distorted from ideal D3h to approximate C2 symmetry by compression along a C2 axis in the plane of the ring. All Fe-Cd distances are equal within experimental error [2.640 (7) {\AA}]. The Cd-Fe-Cd angles vary from 138.81 (15) to 148.40 (15)°, and the Fe-Cd-Fe angles from 94.78 (14) to 102.04 (16)°. The iron coordination geometry is significantly distorted from an octahedral one toward a tetrahedral one in which cadmium atoms cap two of the faces. There is evidence for a weak semibridging interaction between carbonyl carbon and cadmium atoms. The Cd-Fe bonding in [(bpy)CdFe(CO)4]3 appears to be more ionic than in [CdFe(CO)4]4. The trimeric compound dissociates in benzene solution.",
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N2 - The complex (bpy)CdFe(CO)4 crystallizes from hot 1,2,4-trichlorobenzene as a trimer with the stoichiometry [(bpy)CdFe(CO)4]3·3/4C6H 3Cl3. The crystals belong to the tetragonal space group S41-P4 with eight six-membered metal-metal bonded rings and six solvent molecules in a unit cell of dimensions a = b = 29.049 (10), c = 13.241 (5) Å, V = 11 170 Å3. Full-matrix least-squares refinement yielded a final value of the conventional R index (on F) of 0.066 for 5643 reflections having Fo2 > 3σ(Fo2). The molecular structure consists of nearly planar rings of alternating cis-Fe(CO)4 and (bpy)Cd units. The ring is distorted from ideal D3h to approximate C2 symmetry by compression along a C2 axis in the plane of the ring. All Fe-Cd distances are equal within experimental error [2.640 (7) Å]. The Cd-Fe-Cd angles vary from 138.81 (15) to 148.40 (15)°, and the Fe-Cd-Fe angles from 94.78 (14) to 102.04 (16)°. The iron coordination geometry is significantly distorted from an octahedral one toward a tetrahedral one in which cadmium atoms cap two of the faces. There is evidence for a weak semibridging interaction between carbonyl carbon and cadmium atoms. The Cd-Fe bonding in [(bpy)CdFe(CO)4]3 appears to be more ionic than in [CdFe(CO)4]4. The trimeric compound dissociates in benzene solution.

AB - The complex (bpy)CdFe(CO)4 crystallizes from hot 1,2,4-trichlorobenzene as a trimer with the stoichiometry [(bpy)CdFe(CO)4]3·3/4C6H 3Cl3. The crystals belong to the tetragonal space group S41-P4 with eight six-membered metal-metal bonded rings and six solvent molecules in a unit cell of dimensions a = b = 29.049 (10), c = 13.241 (5) Å, V = 11 170 Å3. Full-matrix least-squares refinement yielded a final value of the conventional R index (on F) of 0.066 for 5643 reflections having Fo2 > 3σ(Fo2). The molecular structure consists of nearly planar rings of alternating cis-Fe(CO)4 and (bpy)Cd units. The ring is distorted from ideal D3h to approximate C2 symmetry by compression along a C2 axis in the plane of the ring. All Fe-Cd distances are equal within experimental error [2.640 (7) Å]. The Cd-Fe-Cd angles vary from 138.81 (15) to 148.40 (15)°, and the Fe-Cd-Fe angles from 94.78 (14) to 102.04 (16)°. The iron coordination geometry is significantly distorted from an octahedral one toward a tetrahedral one in which cadmium atoms cap two of the faces. There is evidence for a weak semibridging interaction between carbonyl carbon and cadmium atoms. The Cd-Fe bonding in [(bpy)CdFe(CO)4]3 appears to be more ionic than in [CdFe(CO)4]4. The trimeric compound dissociates in benzene solution.

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