Why is Re-Re bond formation/cleavage in [Re(bpy)(CO)3] 2 different from that in [Re(CO)5]2? Experimental and theoretical studies on the dimers and fragments

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Abstract

The Re(NN)(CO)3(THF) (NN = bpy = 2,2′-bipyridine or dmb = 4,4′-dimethyl-2,2′-bipyridine) radical, produced by homolysis of [Re(NN)(CO)3]2 in THF solution by visible irradiation, dimerizes with rate constants kd = 20 ± 3 and 11 ± 4 M-1 s-1 for NN = dmb and bpy, respectively. The dimerization processes are strikingly slow compared to those of typical metal radicals including Re(CO)5 (kd ≈ 109 M -1 s-1). In order to explain such slow reactions, we have performed B3LYP hybrid DFT and fully ab initio RHF and MP2 calculations on several conformations of [Re(bpy)(CO)3]2 (cis, trans, skewed cis, skewed trans) and [Re(CO)5]2 (staggered) and on their constituent monomer radicals and anions. The calculations show that the most stable geometry of [Re(bpy)(CO)3]2 is skewed cis, and the experimental infrared spectrum and photochemical properties of the [Re(bpy)(CO)3]2 dimer are best described by the calculated properties of the skewed cis conformer in which there is no low-lying unoccupied orbital that is predominantly σMM* in character. The Re(bpy)(CO)3(THF) ligand radical is more stable than the 5-coordinate "17-electron" metal radical, Re(bpy)(CO)3, suggesting that the extremely slow dimerization rate most likely arises from the solvent blocking the binding site (i.e., the estimated fraction of the five-coordinate monomer is 1.6 × 10-2). Theoretical results are consistent with our experimental results that the dimerization process proceeds via the Re centered radical, which is involved in a pre-equilibrium favoring the ligand-centered radical. Furthermore, time-dependent DFT calculations on [Re(bpy)(CO)3]2 and [Re(bpy)(CO)3]- identify the origin of UV-vis absorption in THF.

Original languageEnglish
Pages (from-to)7636-7647
Number of pages12
JournalInorganic Chemistry
Volume43
Issue number24
DOIs
Publication statusPublished - Nov 29 2004

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Carbon Monoxide
Dimers
cleavage
dimers
fragments
dimerization
Dimerization
monomers
Discrete Fourier transforms
ligands
Monomers
Metals
metals
Ligands
infrared spectra
anions
orbitals
irradiation
Anions
Conformations

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

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title = "Why is Re-Re bond formation/cleavage in [Re(bpy)(CO)3] 2 different from that in [Re(CO)5]2? Experimental and theoretical studies on the dimers and fragments",
abstract = "The Re(NN)(CO)3(THF) (NN = bpy = 2,2′-bipyridine or dmb = 4,4′-dimethyl-2,2′-bipyridine) radical, produced by homolysis of [Re(NN)(CO)3]2 in THF solution by visible irradiation, dimerizes with rate constants kd = 20 ± 3 and 11 ± 4 M-1 s-1 for NN = dmb and bpy, respectively. The dimerization processes are strikingly slow compared to those of typical metal radicals including Re(CO)5 (kd ≈ 109 M -1 s-1). In order to explain such slow reactions, we have performed B3LYP hybrid DFT and fully ab initio RHF and MP2 calculations on several conformations of [Re(bpy)(CO)3]2 (cis, trans, skewed cis, skewed trans) and [Re(CO)5]2 (staggered) and on their constituent monomer radicals and anions. The calculations show that the most stable geometry of [Re(bpy)(CO)3]2 is skewed cis, and the experimental infrared spectrum and photochemical properties of the [Re(bpy)(CO)3]2 dimer are best described by the calculated properties of the skewed cis conformer in which there is no low-lying unoccupied orbital that is predominantly σMM* in character. The Re(bpy)(CO)3(THF) ligand radical is more stable than the 5-coordinate {"}17-electron{"} metal radical, Re(bpy)(CO)3, suggesting that the extremely slow dimerization rate most likely arises from the solvent blocking the binding site (i.e., the estimated fraction of the five-coordinate monomer is 1.6 × 10-2). Theoretical results are consistent with our experimental results that the dimerization process proceeds via the Re centered radical, which is involved in a pre-equilibrium favoring the ligand-centered radical. Furthermore, time-dependent DFT calculations on [Re(bpy)(CO)3]2 and [Re(bpy)(CO)3]- identify the origin of UV-vis absorption in THF.",
author = "Etsuko Fujita and James Muckerman",
year = "2004",
month = "11",
day = "29",
doi = "10.1021/ic048910v",
language = "English",
volume = "43",
pages = "7636--7647",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "24",

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T1 - Why is Re-Re bond formation/cleavage in [Re(bpy)(CO)3] 2 different from that in [Re(CO)5]2? Experimental and theoretical studies on the dimers and fragments

AU - Fujita, Etsuko

AU - Muckerman, James

PY - 2004/11/29

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N2 - The Re(NN)(CO)3(THF) (NN = bpy = 2,2′-bipyridine or dmb = 4,4′-dimethyl-2,2′-bipyridine) radical, produced by homolysis of [Re(NN)(CO)3]2 in THF solution by visible irradiation, dimerizes with rate constants kd = 20 ± 3 and 11 ± 4 M-1 s-1 for NN = dmb and bpy, respectively. The dimerization processes are strikingly slow compared to those of typical metal radicals including Re(CO)5 (kd ≈ 109 M -1 s-1). In order to explain such slow reactions, we have performed B3LYP hybrid DFT and fully ab initio RHF and MP2 calculations on several conformations of [Re(bpy)(CO)3]2 (cis, trans, skewed cis, skewed trans) and [Re(CO)5]2 (staggered) and on their constituent monomer radicals and anions. The calculations show that the most stable geometry of [Re(bpy)(CO)3]2 is skewed cis, and the experimental infrared spectrum and photochemical properties of the [Re(bpy)(CO)3]2 dimer are best described by the calculated properties of the skewed cis conformer in which there is no low-lying unoccupied orbital that is predominantly σMM* in character. The Re(bpy)(CO)3(THF) ligand radical is more stable than the 5-coordinate "17-electron" metal radical, Re(bpy)(CO)3, suggesting that the extremely slow dimerization rate most likely arises from the solvent blocking the binding site (i.e., the estimated fraction of the five-coordinate monomer is 1.6 × 10-2). Theoretical results are consistent with our experimental results that the dimerization process proceeds via the Re centered radical, which is involved in a pre-equilibrium favoring the ligand-centered radical. Furthermore, time-dependent DFT calculations on [Re(bpy)(CO)3]2 and [Re(bpy)(CO)3]- identify the origin of UV-vis absorption in THF.

AB - The Re(NN)(CO)3(THF) (NN = bpy = 2,2′-bipyridine or dmb = 4,4′-dimethyl-2,2′-bipyridine) radical, produced by homolysis of [Re(NN)(CO)3]2 in THF solution by visible irradiation, dimerizes with rate constants kd = 20 ± 3 and 11 ± 4 M-1 s-1 for NN = dmb and bpy, respectively. The dimerization processes are strikingly slow compared to those of typical metal radicals including Re(CO)5 (kd ≈ 109 M -1 s-1). In order to explain such slow reactions, we have performed B3LYP hybrid DFT and fully ab initio RHF and MP2 calculations on several conformations of [Re(bpy)(CO)3]2 (cis, trans, skewed cis, skewed trans) and [Re(CO)5]2 (staggered) and on their constituent monomer radicals and anions. The calculations show that the most stable geometry of [Re(bpy)(CO)3]2 is skewed cis, and the experimental infrared spectrum and photochemical properties of the [Re(bpy)(CO)3]2 dimer are best described by the calculated properties of the skewed cis conformer in which there is no low-lying unoccupied orbital that is predominantly σMM* in character. The Re(bpy)(CO)3(THF) ligand radical is more stable than the 5-coordinate "17-electron" metal radical, Re(bpy)(CO)3, suggesting that the extremely slow dimerization rate most likely arises from the solvent blocking the binding site (i.e., the estimated fraction of the five-coordinate monomer is 1.6 × 10-2). Theoretical results are consistent with our experimental results that the dimerization process proceeds via the Re centered radical, which is involved in a pre-equilibrium favoring the ligand-centered radical. Furthermore, time-dependent DFT calculations on [Re(bpy)(CO)3]2 and [Re(bpy)(CO)3]- identify the origin of UV-vis absorption in THF.

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