Spectroscopy and Photochemistry of Ni(CO)2(α-Diimine) Complexes

  • P. C. Servaas
  • D. J. Stufkens
  • A. Oskam
Conference paper

Abstract

During the last ten years much attention has been paid in our laboratory to the spectroscopy, photochemistry and in some cases photophysics of low-valence transition metal α-diimine complexes. For most of these complexes the lowest excited state is metal to α-diimine charge transfer (MLCT) in character. Only in a few cases, viz. d6-M(CO)4 (α-diimine) (M=Cr,Mo,W) (Balk 1980; van Dijk 1985) and recently d8 -Fe(CO)3(α-diimine) (van Dijk, to be published; Kokkes 1984), a reaction was observed from these MLCT states, although the quantum yields of these reactions were always very low (φ<0.01). Because of these low quantum yields and because of the presence of close-lying reactive LF states, photochemical reactions normally occur from these latter states, especially at room temperature when these LF states become thermally occupied.

Keywords

Nickel Chromium Benzene Toluene Tungsten 

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References

  1. Andréa RR, Louwen JN, Kokkes MW, Stufkens DJ, Oskam A, (1985) He(I) and He(II) Photoelectron Spectra of Transition Metal Carbonyl Complexes containing a 1,4-diaza-1,3-butadiene ligand. J. Organomet. Chem. 281: 273–289.CrossRefGoogle Scholar
  2. Balk RW, Snoeck T, Stufkens DJ, Oskam A (1980) (Diimine) Carbonyl Complexes of Chromium, Molybdenum and Tungsten: Relationship between Resonance Raman Spectra and Photosubstitution Quantum Yields. Inorg. Chem. 19: 3015–3021.CrossRefGoogle Scholar
  3. tom Dieck H, Svoboda M, Greiser T (1981) Nickel(O)-bis(chelate) mit Aromatischen N-Substituenten, Z. Naturforsch. 36b: 823–832.Google Scholar
  4. van Dijk HK, Servaas PC, Stufkens DJ, Oskam A (1985) Steric and Electronic Effects on the Quantum Yield of Photosubstitution of CO in W(CO) (α-diimine) Complexes. Inorg. Chim. Acta, 104: 1 79–183.Google Scholar
  5. van Dijk HK, et. al., to be published.Google Scholar
  6. von Hausen HD, Krogmann K (1972) Die Kristallstruktur von Dicarbonyl- diacetylbis(dimethylhydrazon)-Nickel(O). Z. Anorg. Allg. Chem. 389: 247–253.CrossRefGoogle Scholar
  7. Kokkes MW, Stufkens DJ, Oskam A (1984) Photochemistry of Tricarbonyl (α-diimine) iron complexes. J. Chem. Soc., Dalton Trans.: 1005–1017.Google Scholar
  8. Sieler J, Than NN, Benedix R, Dinjus E, Walther D (1985) Kristallstruktur von 4,6-dimethy 1–2,2’-dipyridyl-dicarbonylnickel (O). Z. Anorg. Allg. Chem. 522: 131–136.CrossRefGoogle Scholar
  9. Svoboda M, tom Dieck H, Krüger C, Tsay YH (1981) Nickel (O)-bis- (chelate) mit Aliphatischen N-Substituenten. Z. Naturforsch. 36b: 814–822.Google Scholar

Copyright information

© Springer-Verlag Berlin · Heidelberg 1987

Authors and Affiliations

  • P. C. Servaas
    • 1
  • D. J. Stufkens
    • 1
  • A. Oskam
    • 1
  1. 1.Anorganisch Chemisch LaboratoriumUniversity of AmsterdamAmsterdamThe Netherlands

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