Phosphine-substituted (η5-pentadienyl) manganese carbonyl complexes: Geometric structures, electronic structures, and energetic properties of the associative substitution mechanism, including isolation of the slipped η3-pentadienyl associative intermediate

José Ignacio De La Cruz Cruz, Patricia Juárez-Saavedra, Brenda Paz-Michel, Marco Antonio Leyva-Ramirez, Asha Rajapakshe, Aaron K. Vannucci, Dennis L Lichtenberger, M. Angeles Paz-Sandoval

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Abstract

The molecule (η5-Me2Pdl)Mn(CO)35-Me2Pdl = 2,4-dimethyl-η5- pentadienyl) has been prepared by a new method and used as a starting material to prepare the molecules (η5-Me2Pdl)Mn(CO) n(PMe3)3-n (n = 2, 1) by phosphine substitution for carbonyls. The first carbonyl substitution is achieved thermally in refluxing cyclohexane, and the second carbonyl substitution requires photolysis. At room temperature in benzene the associative intermediate (η3-Me2Pdl)Mn(CO)3(PMe3) that precedes the initial loss of carbonyl is observed. Single-crystal structures are reported for all complexes, including the associative intermediate of the first substitution in which the pentadienyl ligand has slipped to the η3 bonding mode. These molecules offer an opportunity to examine fundamental principles of the interactions between metals and pentadienyl ligands in comparison to the well-developed chemistry of metal cyclopentadienyl (Cp) complexes as a function of electron richness at the metal center. Photoelectron spectra of these molecules show that the Me2Pdl ligand has π ionizations at energy lower than that for the analogous Cp ligand and donates more strongly to the metal than the Cp ligand, making the metal more electron rich. Phosphine substitutions for carbonyls further increase the electron richness at the metal center. Density functional calculations provide further insight into the electronic structures and bonding of the molecules, revealing the energetics and role of the pentadienyl slip from η5 to η3 bonding in the early stages of the associative substitution mechanism. Computational comparison with dissociative ligand substitution mechanisms reveals the roles of dispersion interaction energies and the entropic free energies in the ligand substitution reactions. An alternative scheme for evaluating the computational translational and rotational entropy of a dissociative mechanism in solution is offered.

Original languageEnglish (US)
Pages (from-to)278-288
Number of pages11
JournalOrganometallics
Volume33
Issue number1
DOIs
StatePublished - Jan 13 2014

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phosphine
Manganese
phosphines
Electronic structure
manganese
isolation
Substitution reactions
substitutes
electronic structure
Ligands
ligands
Metals
Carbon Monoxide
Molecules
metals
molecules
Electrons
electrons
Photolysis
Metal complexes

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Phosphine-substituted (η5-pentadienyl) manganese carbonyl complexes : Geometric structures, electronic structures, and energetic properties of the associative substitution mechanism, including isolation of the slipped η3-pentadienyl associative intermediate. / De La Cruz Cruz, José Ignacio; Juárez-Saavedra, Patricia; Paz-Michel, Brenda; Leyva-Ramirez, Marco Antonio; Rajapakshe, Asha; Vannucci, Aaron K.; Lichtenberger, Dennis L; Paz-Sandoval, M. Angeles.

In: Organometallics, Vol. 33, No. 1, 13.01.2014, p. 278-288.

Research output: Contribution to journalArticle

De La Cruz Cruz, José Ignacio ; Juárez-Saavedra, Patricia ; Paz-Michel, Brenda ; Leyva-Ramirez, Marco Antonio ; Rajapakshe, Asha ; Vannucci, Aaron K. ; Lichtenberger, Dennis L ; Paz-Sandoval, M. Angeles. / Phosphine-substituted (η5-pentadienyl) manganese carbonyl complexes : Geometric structures, electronic structures, and energetic properties of the associative substitution mechanism, including isolation of the slipped η3-pentadienyl associative intermediate. In: Organometallics. 2014 ; Vol. 33, No. 1. pp. 278-288.
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abstract = "The molecule (η5-Me2Pdl)Mn(CO)3 (η5-Me2Pdl = 2,4-dimethyl-η5- pentadienyl) has been prepared by a new method and used as a starting material to prepare the molecules (η5-Me2Pdl)Mn(CO) n(PMe3)3-n (n = 2, 1) by phosphine substitution for carbonyls. The first carbonyl substitution is achieved thermally in refluxing cyclohexane, and the second carbonyl substitution requires photolysis. At room temperature in benzene the associative intermediate (η3-Me2Pdl)Mn(CO)3(PMe3) that precedes the initial loss of carbonyl is observed. Single-crystal structures are reported for all complexes, including the associative intermediate of the first substitution in which the pentadienyl ligand has slipped to the η3 bonding mode. These molecules offer an opportunity to examine fundamental principles of the interactions between metals and pentadienyl ligands in comparison to the well-developed chemistry of metal cyclopentadienyl (Cp) complexes as a function of electron richness at the metal center. Photoelectron spectra of these molecules show that the Me2Pdl ligand has π ionizations at energy lower than that for the analogous Cp ligand and donates more strongly to the metal than the Cp ligand, making the metal more electron rich. Phosphine substitutions for carbonyls further increase the electron richness at the metal center. Density functional calculations provide further insight into the electronic structures and bonding of the molecules, revealing the energetics and role of the pentadienyl slip from η5 to η3 bonding in the early stages of the associative substitution mechanism. Computational comparison with dissociative ligand substitution mechanisms reveals the roles of dispersion interaction energies and the entropic free energies in the ligand substitution reactions. An alternative scheme for evaluating the computational translational and rotational entropy of a dissociative mechanism in solution is offered.",
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T2 - Geometric structures, electronic structures, and energetic properties of the associative substitution mechanism, including isolation of the slipped η3-pentadienyl associative intermediate

AU - De La Cruz Cruz, José Ignacio

AU - Juárez-Saavedra, Patricia

AU - Paz-Michel, Brenda

AU - Leyva-Ramirez, Marco Antonio

AU - Rajapakshe, Asha

AU - Vannucci, Aaron K.

AU - Lichtenberger, Dennis L

AU - Paz-Sandoval, M. Angeles

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AB - The molecule (η5-Me2Pdl)Mn(CO)3 (η5-Me2Pdl = 2,4-dimethyl-η5- pentadienyl) has been prepared by a new method and used as a starting material to prepare the molecules (η5-Me2Pdl)Mn(CO) n(PMe3)3-n (n = 2, 1) by phosphine substitution for carbonyls. The first carbonyl substitution is achieved thermally in refluxing cyclohexane, and the second carbonyl substitution requires photolysis. At room temperature in benzene the associative intermediate (η3-Me2Pdl)Mn(CO)3(PMe3) that precedes the initial loss of carbonyl is observed. Single-crystal structures are reported for all complexes, including the associative intermediate of the first substitution in which the pentadienyl ligand has slipped to the η3 bonding mode. These molecules offer an opportunity to examine fundamental principles of the interactions between metals and pentadienyl ligands in comparison to the well-developed chemistry of metal cyclopentadienyl (Cp) complexes as a function of electron richness at the metal center. Photoelectron spectra of these molecules show that the Me2Pdl ligand has π ionizations at energy lower than that for the analogous Cp ligand and donates more strongly to the metal than the Cp ligand, making the metal more electron rich. Phosphine substitutions for carbonyls further increase the electron richness at the metal center. Density functional calculations provide further insight into the electronic structures and bonding of the molecules, revealing the energetics and role of the pentadienyl slip from η5 to η3 bonding in the early stages of the associative substitution mechanism. Computational comparison with dissociative ligand substitution mechanisms reveals the roles of dispersion interaction energies and the entropic free energies in the ligand substitution reactions. An alternative scheme for evaluating the computational translational and rotational entropy of a dissociative mechanism in solution is offered.

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