Abstract
Photochemically generated 17-valence electron metal radicals react with ligands to form 19-electron complexes, e.g., reaction 1 [1]. The 19-electron complexes are versatile reducing agents and we reported that they can be used to reduce a variety or organic, organometallic, and inorganic complexes, e.g., reaction 2. In addition to their versatility, two other features make the 19-electron complexes ideal choices as reducing agents for many applications. First, the complexes are easy to generate: the metal-metal bonded dimers are convenient precursors and the wavelength of irradiation (λ > 500 nm) generally precludes substrate absorption. Second, the 19-electron complexes are powerful reducing agents. In some cases, we estimate their oxidation potential to be 2 V or higher.
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
Tyler, D. R. (1991) 19-Electron organometallic adducts, Acc. Chem. Res. 24, 325–331.
Barton, M. and Atwood, J. D. (1991) Aqueous soluble organometallic complexes, J. Coord. Chem. 24, 43–67.
MacKenzie, V. and Tyler, D. R. (1987) Reduction of water-soluble substrates in micellar solutions using photochemically generated nineteen-electron organometallic complexes, J. Chem. Soc., Chem. Common. 1783–1784.
Avey, A. and Tyler, D. R. (1992) Synthesis and photochemistry of the aqueous-soluble [(CpCH2CH2NH3+)2Mo2(CO)6] complex. Generation of 19-electron complexes in aqueous solution, Organometallics 11, 3856–3863.
Avey, A., Tenhaeff, S. C., Weakley, T. J. R., and Tyler, D. R. (1991) Organometallic photochemistry in aqueous solution. Synthesis, crystal and molecular structure, and photochemistry of the (CpCOOH)2W2(CO)6 complex. Generation of 19-electron organometallic complexes in aqueous solution and their use as reducing agents. Photochemical production of hydrogen, Organometallics 10, 3607–3613.
Macomber, D. W. and Rausch, M. D. (1993) Functionally substituted cyclopentadienyl-tricarbonylmethyl derivatives of chromium, molybdenum, and tungsten, J. Organomet. Chem. 258, 331–341.
Birdwhistell, R., Hackett, P., and Manning, A. R. (1978) A simple and effective preparation of (η-RC5H4)2M2(CO)6 complexes (M = Cr, Mo and W), J. Organomet. Chem. 157, 239–241.
Meyer, T. J. and Caspar, J. V. (1985) Photochemistry of metal-metal bonds, Chem. Rev. 85, 187–218.
Avey, A., Weakley, T. J. R., and Tyler, D. R. (1993) Supramolecular photochemistry of the [(CpCH2CH2NH3 +)2Mo2(CO)6][PF6 -]2 complex. Chemical ramifications of a tentacle ligand covalently bonded nearby to a reactive metal center, J. Am. Chem. Soc. 115, 7706–7715.
Darensbourg, M. Y. and Daigle, D. (1975) Synthesis and spectral properties of metal carbonyl derivatives of the tetrabasic, nonchelating phosphatriazaadamantane ligand, Inorg. Chem. 14,1217–1218.
Avey, A., Schut, D. M., Weakley, T. J. R., and Tyler, D. R. (1993) A new water-soluble phosphine for use in aqueous organometallic systems. Products for the reactions of 2,3-bis(diphenylphosphino)maleic anhydride with water and oxygen, Inorg. Chem. 32, 233–236.
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1995 Springer Science+Business Media Dordrecht
About this chapter
Cite this chapter
Tyler, D.R. (1995). Organometallic Radical Chemistry in Aqueous Solution. In: Horváth, I.T., Joó, F. (eds) Aqueous Organometallic Chemistry and Catalysis. NATO ASI Series, vol 5. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-0355-8_5
Download citation
DOI: https://doi.org/10.1007/978-94-011-0355-8_5
Publisher Name: Springer, Dordrecht
Print ISBN: 978-94-010-4158-4
Online ISBN: 978-94-011-0355-8
eBook Packages: Springer Book Archive