Transition metal complexes, excited

For transitiog+metal complexes an intense eel as it was observed for Ru(bipy) seems to be rather an exception. It is certainly difficult to draw definite mechanistic conclusions based on small eel efficiencies because eel may originate from side reactions in these cases. However, our results do show that electron transfer reactions with large driving forces can generate electronically excited transition metal complexes as a rather general phenomenon. 

In this review article, we discuss the fundamental basis of the bimolecular electron-transfer reactions of electronically excited transition metal complexes and then collect and examine the data so far obtained in this field. Although a wide range of systems are discussed, we focus primarily on quantitative studies, the majority of which involves Werner-type complexes in fluid solution. 

Recently, attempts have been made to formulate theoretical models upon which the primary chemical decay processes of electronically excited transition metal complexes may be qualitatively interpreted and predicted. The attempts have focused primarily on the substitutional behavior of ligand field excited state compounds (42-48) and the redox processes associated with LMCT excited states (34). 

INORGANIC COMPLEXES. The cis-trans isomerization of a planar square form of a rt transition metal complex (e.g., of Pt " ) is known to be photochemically allowed and themrally forbidden [94]. It was found experimentally [95] to be an inhamolecular process, namely, to proceed without any bond-breaking step. Calculations show that the ground and the excited state touch along the reaction coordinate (see Fig. 12 in [96]). Although conical intersections were not mentioned in these papers, the present model appears to apply to these systems. 

The coordination chemistry of CO2 is by no means as extensive as that of CO (p. 926) but some exciting developments have recently been published. The first transition metal complexes with CO2 were claimed by... 

Vogler, A., Kunkeley, H. Photochemistry of Transition Metal Complexes Induced by Outer-Sphere Charge Transfer Excitation. 158, 1-30 (1990). 

Relaxation of excited states in transition-metal complexes. M. K. DeArmond, Acc. Chem. Res., 1974,7,309-315(39). 

The finding of preparatively available iminoboranes RB = NR some years ago opened exciting new possibilities not only in B—N chemistry, but also in coordination chemistry. The first examples of iminoborane-transition-metal complexes have now been published. The structurally completely characterized t-BuB = NBu-t adds, like its alkyne analog, to the 03(00)5 fragment as a bridging ligand. When Co2(CO)g and t-BuB = NBu-t are dissolved in pentane at 0°C, warming to RT and evaporation of unreacted iminoborane yields (t-BuBNBu-t)Co2(CO)5 (86%) as a black solid, which can be recrystallized from ether-nitromethane (1 3) ... 

Busch DH (2005) First Considerations Principles, Classification, and History. 249 in press Bussiere G, Beaulac R, Belisle H, Lescop C, Luneau D, Rey P, Reber C (2004) Excited States and Optical Spectroscopy of Nitronyl Nitroxides and Their Lanthanide and Transition Metal Complexes. 241 97-118 Cadierno V, see Majoral J-P (2002) 220 53-77 Camara M, see Chhabra SR (2005) 240 279-315 Caminade A-M, see Majoral J-P (2003) 223 111-159 CantriU SJ, see Arico F (2005) 249 in press... 

PBE dendrimers with a cyclic polyamine core at the focal point have been synthesized to form transition-metal complexes [27]. Tb + complexes exhibited luminescence by the excitation of the dendrons. 

The interconversion between different spin states is closely related to the intersystem crossing process in excited states of transition-metal complexes. Hence, much of the interest in the rates of spin-state transitions arises from their relevance to a better understanding of intersystem crossing phenomena. The spin-state change can alternatively be described as an intramolecular electron transfer reaction [34], Therefore, rates of spin-state transitions may be employed to assess the effect of spin multiplicity changes on electron transfer rates. These aspects have been covered in some detail elsewhere [30]. 

Moreno M, Aramburu JA, Barriuso MT (2003) Electronic Properties and Bonding in Transition Metal Complexes Influence of Pressure 106 127-152 Morita M, Buddhudu S, Rau D, Murakami S (2004) Photoluminescence and Excitation Energy Transfer of Rare Earth Ions in Nanoporous Xerogel and Sol-Gel SiC>2 Glasses 107 115-143... 

Balzani, V., Bolletta, F., Gandolfi, M. T., and Maestri, M. Bimolecular Electron Transfer Reactions of the Excited States of Transition Metal Complexes. 75, 1-64 (1978). 

The information available is discussed in light of the effects of excitation energy and the environment on the photofragmentation process of several transition metal cluster complexes. The photochemical information provides a data base directly relevant to electronic structure theories currently used to understand and predict properties of transition metal complexes (1,18,19). 

A variety of transition metal complexes including organometallics was subjected to an ac electrolysis in a simple undivided electrochemical cell, containing only two current-carrying platinum electrodes. The compounds (A) are reduced and oxidized at the same electrode. If the excitation energy of these compounds is smaller than the potential difference of the reduced (A ) and oxidized (A ) forms, back electron transfer may regenerate the complexes in an electronically excited state (A+ + A A + A). Under favorable conditions an electrochemiluminescence (eel) is then observed (A A + hv). A weak eel appeared upon electrolysis o t]jie following complexes Ir(III)-(2-phenylpyridine-C, N ) [Cu(I)(pyridine)i],... 

Back electron transfer takes place from the electrogenerated reduc-tant to the oxidant near the electrode surface. At a sufficient potential difference this annihilation leads to the formation of excited ( ) products which may emit light (eel) or react "photochemical ly" without light (1,16). Redox pairs of limited stability can be investigated by ac electrolysis. The frequency of the ac current must be adjusted to the lifetime of the more labile redox partner. Many organic compounds have been shown to undergo eel (17-19). Much less is known about transition metal complexes despite the fact that they participate in fljjany redox reactions. 

Neese, F. 2006. Importance of direct spin-spin coupling and spin-flip excitations to the zero-field splittings of transition metal complexes a case study. Journal of the American Chemical Society 128 10213-10222. 

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