Photoelectron spectra and electronic structure of pentacarbonylmanganese halides

Lichtenberger, Dennis L.; Sarapu, Allen C.; Fenske, Richard F.

doi:10.1021/ic50121a048

Cited by 44 publications

(16 citation statements)

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“…Bands five and six have similar positions, areas, and splitting to the Cp e 1 "-based ionizations seen in previously studied piano-stool compounds [56,57] and are assigned as Cp ionizations. The last band is assigned to the Ru-Cl σ ionization (σ) based on the position and band area decrease in going from He I to He II radiation, consistent with FpCl and other metal chlorides [47,58]. None of the band area changes are as large as expected based on pure atomic characters, demonstrating that the distribution of each valence orbital is significantly delocalized throughout the allowed symmetry interactions of the metal with the ligands.…”

Section: Rpcl Ionizationssupporting

confidence: 51%

“…Ionizations from RpC≡CMe [Rp = (η 5 -C 5 H 5 )Ru(CO) 2 ] may also be correlated directly to the ionizations of RpCl, where Cl is known to be a weak π-donor. Photoelectron spectra of metal halides have been the subjects of numerous investigations [47,48], and the well-understood bonding picture from the chloride molecule can be related to RpC≡CMe, with substitution of the alkynyl π x and π y orbitals for the chloride 3p x and 3p y orbitals.…”

Section: Introductionmentioning

confidence: 99%

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Experimental measure of metal–alkynyl electronic structure interactions by photoelectron spectroscopy: (η5-C5H5)Ru(CO)2C CMe and [(η5-C5H5)Ru(CO)2]2(μ-C C)

et al. 2015

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The gas-phase He I and He II photoelectron spectra of the propynylruthenium molecule CpRu(CO) 2 C≡CMe (Cp = η 5-C 5 H 5) and the ethynediyldiruthenium molecule [CpRu(CO) 2 ] 2 (µ-C≡C) are compared with the spectrum of CpRu(CO) 2 Cl to experimentally determine electronic structure interactions of the alkynyl ligands with the metal. The spectra indicate that the interaction between the filled metal-dπ and filled alkynyl-π orbitals dominates the metal-alkynyl π electronic structure, mirroring previously characterized CpFe(CO) 2 alkynyls. All valence ionizations of the Ru molecules are stabilized with respect to similar Fe compounds, contrary to the common expectation of lower ionization energies with atomic substitution down a column of the periodic table. Ab initio electronic structure calculations suggest that this stabilization traces to the greater inherent electronic relaxation energy associated with removal of Fe 3d electrons compared to removal of Ru 4d electrons. Destabilization of the first two ionization bands of the diruthenium molecule are a result of filled-filled interactions between alkynyl π-bonds with the symmetric combination of metal-metal-dπ orbitals, showing electronic communication between the metals through the alkynyl bridge. From the photoelectron spectrum, this communication was calculated to have a minimum electron-transfer integral of 0.56 eV. The stabilization of the antisymmetric combination of the metal-metal-dπ orbitals gives a direct and unique experimental measure of the interaction with the alkynyl π* orbitals. The stabilization caused by the alkynyl π* orbitals was found to be approximately one-third of the destabilization caused by the filled-filled interaction with the alkynyl π-bonds and about one-fourth to one-third the stabilization provided by back-bonding to a carbonyl ligand.

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Section: Rpcl Ionizationssupporting

confidence: 51%

Section: Introductionmentioning

confidence: 99%

Experimental measure of metal–alkynyl electronic structure interactions by photoelectron spectroscopy: (η5-C5H5)Ru(CO)2C CMe and [(η5-C5H5)Ru(CO)2]2(μ-C C)

et al. 2015

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“…The electronic structure of manganese pentacarbonyl halides has been the subject of many theoretical, 9,10 ultraviolet photoelectron spectroscopic (UPS), [11][12][13][14][15][16] and UV-vis spectroscopic studies. 7,[17][18][19] For the present purpose in particular the molecular orbital structure and the excitation spectrum are relevant and will be discussed in section 3.…”

Section: Introductionmentioning

confidence: 99%

Density Functional Study of the Primary Photoprocesses of Manganese Pentacarbonyl Chloride (MnCl(CO)₅)

et al. 1997

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Density functional calculations have been performed on the ground and excited states of MnCl(CO) 5 in order to explain the photochemistry of MX(CO) 5 complexes (M ) Mn, Re; X ) Cl, Br, I). As found earlier for Mn 2 -(CO) 10 (Inorg. Chem. 1996, 35, 2886, the e g -type unoccupied 3d orbitals in the pseudooctahedral environment are located rather high in the virtual orbital spectrum, and the corresponding ligand-field (LF) excitations are more than 1 eV above the lowest excitations. Potential energy curves (PECs) nevertheless show that the lowest excited states, which involve transitions to the Mn-Cl σ* orbital at equilibrium geometry, are dissociative for axial and equatorial CO loss. The mechanism is again, as in Mn 2 (CO) 10 , a strongly avoided crossing of the lowest excited state (a 1,3 E) with the higher dissociative LF states (different ones for CO ax and CO eq dissociation) which rapidly descend upon Mn-CO bond lengthening. In spite of the lowest excitation being to the Mn-Cl σ*-orbital, Mn-Cl homolysis cannot occur out of the lowest excited state. The photochemical behavior of Mn 2 -(CO) 10 , MnH(CO) 5 , and MnCl(CO) 5 is compared. The mechanisms of CO loss are found to be very similar, but there is a large difference with respect to the breaking of the σ bond (Mn-Mn, Mn-H, or Mn-Cl). Only in the case of Mn 2 (CO) 10 , the lowest broad absorption band contains the σ f σ* excitation and leads to σ bond breaking.

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“…100,101 As recognized for cobalt complexes almost 50 years ago, there is an excellent correlation between 59 Co isotropic chemical shifts and l max from UV-visible spectroscopy. 85,102,103 The electronic spectra of many manganese pentacarbonyl compounds have been investigated thoroughly; [104][105][106][107][108][109] however, correlation between electronic transition data and 55 Mn chemical shifts remains unclear. The UV-visible electronic spectra of LMn(CO) 5 (L ¼ CH 3 , H, Cl, Br, I) were first reported in 1963 107 and reinvestigated in 1971 by Blakney and Allen.…”

Section: Resultsmentioning

confidence: 99%

“…104 Over the following decades interpretation of manganese pentacarbonyl halide electronic spectra has been refined. 104,107,108 Despite the many investigations, however, the ordering of the Mn valence orbitals was unclear. 105,108,[110][111][112][113] A recent reinvestigation of the electronic ionization spectra appears to have resolved the remaining uncertainties for BrMn(CO) 5 .…”

Section: Resultsmentioning

confidence: 99%

A solid-state 55Mn NMR spectroscopy and DFT investigation of manganese pentacarbonyl compounds

Feindel

Ooms

Wasylishen

2007

Phys. Chem. Chem. Phys.

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Central transition (55)Mn NMR spectra of several solid manganese pentacarbonyls acquired at magnetic field strengths of 11.75, 17.63, and 21.1 T are presented. The variety of distinct powder sample lineshapes obtained demonstrates the sensitivity of solid-state (55)Mn NMR to the local bonding environment, including the presence of crystallographically unique Mn sites, and facilitates the extraction of the Mn chemical shift anisotropies, CSAs, and the nuclear quadrupolar parameters. The compounds investigated include molecules with approximate C(4v) symmetry, LMn(CO)(5)(L = Cl, Br, I, HgMn(CO)(5), CH(3)) and several molecules of lower symmetry (L = PhCH(2), Ph(3-n)Cl(n)Sn (n= 1, 2, 3)). For these compounds, the Mn CSA values range from <100 ppm for Cl(3)SnMn(CO)(5) to 1260 ppm for ClMn(CO)(5). At 21.1 T the (55)Mn NMR lineshapes are appreciably influenced by the Mn CSA despite the presence of significant (55)Mn quadrupolar coupling constants that range from 8.0 MHz for Cl(3)SnMn(CO)(5) to 35.0 MHz for CH(3)Mn(CO)(5). The breadth of the solid-state (55)Mn NMR spectra of the pentacarbonyl halides is dominated by the CSA at all three applied magnetic fields. DFT calculations of the Mn magnetic shielding tensors reproduce the experimental trends and the magnitude of the CSA is qualitatively rationalized using a molecular orbital, MO, interpretation based on Ramsey's theory of magnetic shielding. In addition to the energy differences between symmetry-appropriate occupied and virtual MOs, the d-character of the Mn MOs is important for determining the paramagnetic shielding contribution to the principal components of the magnetic shielding tensor.

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Photoelectron spectra and electronic structure of pentacarbonylmanganese halides

Abstract: Acknowledgment. We gratefully acknowledge the assistance of L. O. Gilpatrick, who provided the sample of NaBF3OH used in this work.

Cited by 44 publications

References 4 publications

Experimental measure of metal–alkynyl electronic structure interactions by photoelectron spectroscopy: (η5-C5H5)Ru(CO)2C CMe and [(η5-C5H5)Ru(CO)2]2(μ-C C)

Experimental measure of metal–alkynyl electronic structure interactions by photoelectron spectroscopy: (η5-C5H5)Ru(CO)2C CMe and [(η5-C5H5)Ru(CO)2]2(μ-C C)

Density Functional Study of the Primary Photoprocesses of Manganese Pentacarbonyl Chloride (MnCl(CO)₅)

A solid-state 55Mn NMR spectroscopy and DFT investigation of manganese pentacarbonyl compounds

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Photoelectron spectra and electronic structure of pentacarbonylmanganese halides

Abstract: Acknowledgment. We gratefully acknowledge the assistance of L. O. Gilpatrick, who provided the sample of NaBF3OH used in this work.

Cited by 44 publications

References 4 publications

Experimental measure of metal–alkynyl electronic structure interactions by photoelectron spectroscopy: (η5-C5H5)Ru(CO)2C CMe and [(η5-C5H5)Ru(CO)2]2(μ-C C)

Experimental measure of metal–alkynyl electronic structure interactions by photoelectron spectroscopy: (η5-C5H5)Ru(CO)2C CMe and [(η5-C5H5)Ru(CO)2]2(μ-C C)

Density Functional Study of the Primary Photoprocesses of Manganese Pentacarbonyl Chloride (MnCl(CO)5)

A solid-state 55Mn NMR spectroscopy and DFT investigation of manganese pentacarbonyl compounds

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Density Functional Study of the Primary Photoprocesses of Manganese Pentacarbonyl Chloride (MnCl(CO)₅)