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Matrix Photochemistry Of Transition Metal Complexes: Principles, Applications and Links to Other Methods

  • Chapter
Low Temperature Molecular Spectroscopy

Part of the book series: NATO ASI Series ((ASIC,volume 483))

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Abstract

The importance of matrix isolation in laying fundamental principles of transition metal chemistry is illustrated by the discoveries of metal-alkane and metal-xenon bonds, both made in the 1970’s by matrix photochemistry and now subject to wide ranging research by other methods [1 – 5]. The formation of metal carbonyls with non-transition metals represents another illustration. Matrix isolation experiments demonstrated the possibilities for main group complexes as early as 1972 [6 – 7]. In the last two years, methods have been developed for synthesising such species at ambient temperature: several of them prove stable [8 – 10]. Metal carbonyls are no longer the exclusive domain of transition metals. Matrix isolation continues to play an important role: examples of recent developments include oxidative addition of methane to transition metal complexes, isomerisation of metal ethene complexes and metal carbene complexes. At its most effective, matrix isolation is employed in conjunction with other techniques for studying synthesis, spectroscopy or mechanism. Although carbonyl complexes are far easier to study than other transition metal complexes because of their intense characteristic CO-stretching bands, excellent results have been obtained with no carbonyl groups, e.g. for metal porphyrin dioxygen complexes [11], for reactive metallocenes and for metal ethene complexes. This review will build on the principles of matrix isolation developed in the chapter by Downs (q.v.). It will concentrate on photochemical methods of generating unstable species. The importance of links to techniques other than matrix isolation will be developed in the later sections of the chapter. The reader is referred to reviews elsewhere for more details [12 – 17].

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  1. Department of Chemistry, University of York, YO1 5DD, York, UK

    Robin N. Perutz

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  1. Department of Chemistry, University of Coimbra, Coimbra, Portugal

    R. Fausto

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Perutz, R.N. (1996). Matrix Photochemistry Of Transition Metal Complexes: Principles, Applications and Links to Other Methods. In: Fausto, R. (eds) Low Temperature Molecular Spectroscopy. NATO ASI Series, vol 483. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-0281-7_3

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  • DOI: https://doi.org/10.1007/978-94-009-0281-7_3

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