Abstract
Sandwich complexes of transition metals represent one of the most important classes of organometallics. The high chemical and catalytic reactivities of these compounds have stimulated interest in their electronic structures. The nature and the order of the highest occupied molecular orbitals (MOs) in sandwich molecules have been established on the basis of MO calculations, magnetic measurements and photoelectron spectroscopy. As an example, a qualitative MO scheme derived for bis(16-benzene)chromium on the basis of a MS Xa MO calculations, magnetic measurements and photoelectron spectroscopy. As an example, a qualitative MO scheme derived for bis(η6-benzene)chromium on the basis of a MS Xα MO calculation [1] and the photoelectron data [2] is given in Figure 1.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
Weber, J., Geoffroy, M., Goursot, A., and Penigault, E. (1978) Application of multiple scattering Xa molecular orbital method to the determination of the electronic structure of metallocene compounds. 1. Dibenzenechromium and its cation, J. Am. Chem. Soc. 100, 3995–4003.
Brennan, J.G., Cooper, G., Green, J.C., Kaltsoyannis, N., MacDonald, M.A., Payne, M.P., Redfern, C.M., and Sze, K.H. (1992) Electron localization in the bis-arene complexes [(ri-C6H6)2Cr] and [(i-C6H5Me)2Mo]: an investigation by photoelectron spectroscopy with variable photon energy, Chem. Phys 164271–281
Clack, D.W. and Warren, K.D. (1980) Metal-ligand bonding in 3d sandwich complexesStruct. Bond. (Berlin) 391–41
Green, J.C. (1981) Gas phase photoelectron spectra of d-and f-block organometallic compoundsStruct. Bond. (Berlin) 4337–112
Warren, K.D. (1976) Ligand field theory of metal sandwich complexesStruct. Bond. (Berlin) 2745–159
Nagano, Y., Achiba, Y., and Kimura, K. (1986) UV multiphoton dissociation of volatile iron complexes as revealed by MPI ion-current and photoelectron spectroscopyJ. Phys. Chem. 901288–1293
Ray, U., Hou, H.Q., Zhang, Z., Schwarz, W., and Vernon, M. (1989)A crossed laser-molecular beam study of the one and two photon dissociation dynamics of ferrocene at 193 and 248 nmJ. Chem. Phys 904248–4257
Opitz, J. and Harter, P. (1992) Multiphoton ionization of vanadocene and ferrocene at 248 and 193 nm. Wavelength-dependent competition between dissociation and ionizationInt. J. Spectrom. Ion Proc 121183–199
Opitz, J., Bruch, D., and Vonbunau, G. (1993) Multiphoton excitation of ferrocene and vanadocene at 351 nm in comparison with 248 nm and 193 mn. Wavelength-dependent competition between ionization and dissociationOrg. Mass Spectrom 28405–411
Opitz, J., Bruch, D., and Vonbunau, G. (1993) Nanosecond laser excitation of benzene chromium tricarbonyl and dibenzene chromium at 351 nm, 248 mn and 193 nm. Wave-length-dependent competition between ionization and dissociationInt. J. Mass. Spectrom. Ion Proc 125215–228
Berry, R.S. (1961) Ultraviolet spectrum of dibenzene chromium vapor, JChem. Phys 352025–2028
Armstrong, A.T., Smith, F., Elder, E., and McGlynn, S.P. (1967) Electronic absorption spectrum of ferroceneJ. Chem. Phys 464321–4328
Richer, G. and Sandorfy, C. (1985) The far-ultraviolet absorption spectra of ferrocene, cobaltocene, and nickeloceneJ. Mol. Struct 123317–327
Ketkov, S.Y., Domrachev, G.A., and Razuvaev, G.A. (1989) Rydberg series in the near-UV vapour-phase absorption spectra of (î16-Arene)2Cr(0) and (16- Arene)2V(0) complexes, JMol. Struct 195175–188
Ketkov, S.Y. and Domrachev, G.A. (1990) Electronic absorption spectra of molybdenum(0) bisarene complexes,(r16-Arene)2Mo0 J. Organomet. Chem 389187–195
Ketkov, S.Y. and Domrachev, G.A. (1990) Rydberg transitions in the near-ultraviolet vapor-phase absorption spectra of 3d metallocenesInorg. Chico. Acta 178233–242
Ketkov, S.Y. and Domrachev, G.A. (1991) Ultraviolet vapour-phase absorption spectra of d6metallocenesJ. Organomet. Chem 42067–77
Ketkov, S.Y. (1992) Vapor-phase electronic absorption spectrum of (r15-cyclopentadienyl) 17-cycloheptatrienyl)chromium, J. Organomet. Chem.. 429, C38–C40.
Ketkov, S.Y. (1994) Photoabsorption study of electronic excited states of (15cyclopentadienyl)(16-arene)manganese, J. Organomet. Chem. 465, 225–231.
Ketkov, S.Y. (1994) Nature of low-lying electron excited states of (r15-cyclopentadienyl) (17-cycloheptatrienyl)niobium, Russ. Chem. Bull. 43, 583–587.
Green, J.C., Green, M.L.H., Field, C.N., Ng, D.K.P., and Ketkov, S.Y. (1995) Combined photoelectron-photoabsorption study of (r1-cycloheptatrienyl)(r1cyclopentadienyl)tungsten, J. Organomet. Chem. 501, 107–115.
Ketkov, S.Y., Mehnert, C., and Green, J.C. (1996) Electronic excited states of bis(r16- arene)tungsten: an investigation by ultraviolet photoabsorption spectroscopy in the and solution phases, Chem. Phys. 203, 245–255.
Green, J.C. and Ketkov, S.Y. (1996) Electronic structures of 17-cycloheptatrienyl1.17- cyclopentadienyl derivatives of vanadium and tantalum as studied by solution-phase and -phase photoabsorption spectroscopy in the ultraviolet and visible regions, Organometallics 15, 4747–4754.
Ketkov, S.Y., Green, J.C., and Mehnert, C.P. (1997) Rydberg transitions in bis(r16benzene)chromium: a study of isotopic effects and vibronic structures, J. Chem. Soc., Faraday Trans. 93, 2461–2466.
Ketkov, S.Y. and Green, J.C. (1997) Rydberg structures in the gas-phase electronic absorption spectra of ri-cycloheptatrienyl r1-cyclopentadienyl complexes of molybdenum, J. Chem. Soc., Faraday Trans. 93, 2467–2471.
Ketkov, S.Y., Domrachev, G.A., Mehnert, C.P., and Green, J.C. (1998) Structures of Rydberg transitions in the absorption spectra of methyl-substituted derivatives of bis(16- benzene)chromium, Russ. Chem. Bull. 47, 868–874.
Robin, M.B. (1985) Higher excited states of polyatomic molecules, Academic Press, New York.
Penner, A., Amirav, A., Tasaki, S., and Bersohn, R. (1993) Photodissociation and photoionization and their branching ratio in bisbenzene chromium, J Chem. Phys., 99, 176–183.
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2000 Springer Science+Business Media Dordrecht
About this paper
Cite this paper
Ketkov, S.Y. (2000). A Study of Rydberg Bands in the Photoabsorption Spectra of Sandwich Organometallics: The First Step to the Investigation of Multiphoton Processes in the Organometallic Molecules. In: Kajzar, F., Agranovich, M.V. (eds) Multiphoton and Light Driven Multielectron Processes in Organics: New Phenomena, Materials and Applications. NATO Science Series, vol 79. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-4056-0_37
Download citation
DOI: https://doi.org/10.1007/978-94-011-4056-0_37
Publisher Name: Springer, Dordrecht
Print ISBN: 978-0-7923-6272-2
Online ISBN: 978-94-011-4056-0
eBook Packages: Springer Book Archive