Transition-metal complexes, mechanisms photochemical reactions

A major problem in postulating silylenoid metal complexes as intermediates in the redistribution reactions is simply that good model compounds are lacking, and the decomposition mechanisms of silyl transition metal complexes have not been systematically investigated. While there is evidence for transient R2Si species produced by thermal or photochemical means (80-83), there are no known monomeric silylene metal complexes. Several monomeric stannylene and germylene complexes are... 

In Chapter 11, Molecular Electron Transfer, the broad and deep field of electron-transfer reactions of metal complexes is surveyed and analyzed. In Chapter 12, Electron Transfer From the Molecular to the Nanoscale, the new issues arising for electron-transfer processes on the nanoscale are addressed this chapter is less a review than a toolbox for approaching and analyzing new situations. In Chapter 13, Magnetism From the Molecular to the Nanoscale, the mechanisms and consequences of magnetic coupling in zero- and one-dimensional systems comprised of transition-metal complexes is surveyed. Related to the topics covered in this volume are a number addressed in other volumes. The techniques used to make the measurements are covered in Section I of Volume 2. Theoretical models, computational methods, and software are found in Volume 2, Sections II and III, while a number of the case studies presented in Section IV are pertinent to the articles in this chapter. Photochemical applications of metal complexes are considered in Volume 9, Chapters 11-16, 21 and 22. 

Mechanisms of Photochemical Reactions of Transition-Metal Complexes Elucidated hy Pulse Radiolysis Experiments... 

Previously reported work demonstrated that substituents can be used to tune the energies of excited states responsible for the emission spectra of certain group VIII metal complexes (1) and to modify significantly the absorption spectra of complexes displaying metal-to-ligand charge transfer (MLCT) bands (2). In this presentation, we summarize some recent attempts to use ligand substituents in our studies of transition metal complex photochemical reaction mechanisms. The particular subjects of interest are the metal ammine complexes M(NH3)5L where M is Rh(III) or Ru(II) and L is a meta- or para-substituted pyridine. 

Many more examples have been collected for the reaction of transition metal hydride complexes with 1,3-dienes, which appear to proceed via radical pair mechanisms, even without photochemical activation72-77. The following general mechanism has been assumed to be operative for the reaction of HMn(CO)572,73, HFe(CO)4SiCl374,75, HFe(CO)2Cp76 and HCo(CO)4 (H-[M]) (equation 18)77. 

We hope that this review has shown that ever more elaborate experimental and computational techniques continue to be applied to elucidate the structure, assign spectra, and rationalize photochemical reaction mechanisms in transition metal carbonyl complexes. These systems provide a wealth of fascinating vibronically induced chemistry that we are only beginning to understand, and it is expected that as experimental and computational techniques further evolve many more studies of these systems will take place. Transition metal carbonyl systems are of primary importance in organometallic chemistry and unsaturated complexes are of key importance in industrial synthesis. Their photochemistry has many aspects that require a true multi-disciplinary approach, requiring knowledge and expertise in the fields of transition metal chemistry, ultrafast spectroscopy, computational spectroscopy, computational photochemistry and conical intersection theory, Jahn-Teller... 

As discussed in the previous section, a ligand-to-metal charge-transfer transition of the surface complex (mechanism 1) and/or a Fe -O"11 charge-transfer of hematite (mechanism 2) are the oscillators involved in the surface photoredox reaction, leading to reductive dissolution of hematite in the presence of oxalate. The elementary steps and the derivations of the rate expressions of photochemical surface iron(II) formation of mechanism 1 and 2 are outlined in reactions 16-19, Eqs. 20-26, reactions 27-31, and Eqs. 32-37, respectively. 

We and others have used pulse radiolysis methods to clarify a number of complex photochemical mechanisms. In the course of these studies we have also been able to learn a great deal of new chemistry, including the electronic absorption spectra, thermodynamics, and reaction mechanisms of highly reactive transition-metal centers in both unusually high and low oxidation states. As these data pertain to aqueous media, they contribute in an important way to future work on solar photoconversion in water (the ideal medium from both economic and environmental points of view) and to catalysis in aqueous media in general. 

Recent work (20, 21) in our laboratory has focused upon the use of transition metal compounds to sensitize the energy-storing valence isomerization of norbornadiene, NBD, to quadricyclene, Q (Reaction 3). In particular we have found that a catalytic amount of CuCl functions as an effective and quite specific sensitizer for this transformation. Conversions of greater than 90% have been achieved since Cu(I) is ineffective as a catalyst for the energy-releasing reverse reaction. Spectral and photochemical evidence support a mechanism which features a 1 1 ClCu—NBD complex as the photoactive species. As illustrated in Figure 3, an obvious consequence of complexation is a shift of the absorption spectrum of the system into a region accessible to the 313-nm irradiation used. Possible pathways by which the photo-excited complex relaxes to Q have been discussed (12). 

Iron porphyrin carbenes and vinylidenes are photoactive and possess a unique photochemistry since the mechanism of the photochemical reaction suggests the Hberation of free carbene species in solution [ 110,111 ]. These free carbenes can react with olefins to form cyclopropanes (Eq. 15). The photochemical generation of the free carbene fragment from a transition metal carbene complex has not been previously observed [112,113]. Although the photochemistry of both Fischer and Schrock-type carbene has been investigated, no examples of homolytic carbene dissociation have yet been foimd. In the case of the metalloporphyrin carbene complexes, the lack of other co-ordinatively labile species and the stability of the resulting fragment both contribute to the reactivity of the iron-carbon double bond. Thus, this photochemical behavior is quite different to that previously observed with other classes of carbene complexes [113,114]. 

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