Photoinduced elimination

Photoinduced Elimination of from MoH (dppe) and MoH4(PPh2Me)4... 

The photoinduced -elimination of 1,2,3-triazole from 1-(A,A-bisacyl)amino-l,2,3-triazoles (142), itself formed from the photochemical isomerization of triazoles (141), proceeds either via an intra-or intermolecular hydrogen abstraction or electron-transfer mechanism followed by homolytic cleavage of the A,A-bond (path a) or via t -assisted )8-cleavage of the same weak bond (path b). The composition of the products suggests that in all cases a c-type 1,2,3-triazolyl radical (143) is eliminated which is further quenched by hydrogen abstraction as shown in Scheme 24 <93JHC1301>. 

The photochemical studies of transition metal hydride complexes that have appeared in the chemical literature are reviewed, with primary emphasis on studies of iridium and ruthenium that were conducted by our research group. The photochemistry of the molybdenum hydride complexes Mo(tj5-C5H5)2M2] and [MoH4(dppe)2] (dppe = Ph2PCH2CH2PPh2), which eliminate H2 upon photolysis, is discussed in detail. The photoinduced elimination of molecular hydrogen from di-and polyhydride complexes of the transition elements is proposed to be a general reaction pathway. 

Mo(r75-C5H5)2H2] and [MoH dppe ]. Our studies of the di- and trihydride complexes of ruthenium and iridium, described above and published previously (27,35), and those of other workers (discussed at the beginning of this chapter), indicate that photoinduced elimination of molecular hydrogen is a common reaction pathway for di- and polyhydride complexes. To demonstrate the photoreaction s generality and its utility for generating otherwise unattainable, extremely reactive metal complexes, we have begun to study the photochemistry of polyhydride complexes of the early transition metals. We focused initially... 

In fact, photoinduced elimination of CO from CpM(CO)2R complexes has been used extensively to synthesize mono- and disubstituted derivatives with a number of different entering ligands [Eq. (90)]. The nature and... 

Photoinduced elimination of carbon monoxide from metal carbonyls has been treated in Section 5.1. 

An example of the photoinduced elimination of hydrogen with subsequent ligand coordination to give a coordinately saturated complex as product is found in die conversion of RuH2(CO)(PPh3>3 into Ru(CO)3(PPh3)3 in the presence of CO (Ref. 168) ... 

Photochemical elimination reactions include all those photoinduced reactions resulting in the loss of one or more fragments from the excited molecule. Loss of carbon monoxide from type I or a-cleavage of carbonyl compounds has been previously considered in Chapter 3. Other types of photoeliminations, to be discussed here, include loss of molecular nitrogen from azo, diazo, and azido compounds, loss of nitric oxide from organic nitrites, and loss of sulfur dioxide and other miscellaneous species. 

Successive hydrogen transfers within 60, followed by coordination of olefin and then H2 (an unsaturate route), constitute the catalytic cycle, while isomerization is effected through HFe(CO)3(7r-allyl) formed from 59. Loss of H2 from 60 was also considered to be photoinduced, and several hydrides, including neutral and cationic dihydrides of iridium(III) (385, 450, 451), ruthenium(II) (452) and a bis(7j-cyclopentadienyltungsten) dihydride (453), have been shown to undergo such reductive elimination of hydrogen. Photoassisted oxidative addition of H2 has also been dem-... 

Photoinduced reductive elimination of from polyhydride complexes, HxMLn (x > 3) can, in principle, lead to the generation... 

This has implications for the design of high-surface-area solar cells in general If the bulk of the device is essentially field-free at equilibrium, then mobile electrolyte and nanoporosity are required to eliminate the photoinduced electric fields that would otherwise inhibit charge-carrier separation. On the other hand, if the particle size is substantially larger than in the conventional dye cell or if there is no mobile electrolyte, then an interfacial or bulk built-in electric field... 

The interface model predicts that Vcx in a dye cell will not be limited by because does not control the charge-separation process. Rather than having large potential gradients at equilibrium, as in conventional cells, the DSSC has only small and relatively insignificant values of and xbl. Illumination of a DSSC causes the potential gradients to increase, whereas in a conventional cell, they decrease upon illumination. Because the photoinduced increase in is practically eliminated by electrolyte ion redistribution, the photoinduced increase in p,neq can drive an efficient photoconversion process. 

The entire photolysis sequence can be reversed readily by H2, as summarized in Scheme 1 (27). A sealed, degassed benzene solution of [IrClH2(PPh3)3], from which the photoreleased H3 is not allowed to escape, can be cycled repeatedly (>50 cycles) through the photoinduced H2 elimination-thermal H2 addition reactions without any observable loss of complex. Elimination of H2 can be induced by irradiation with X < 400 nm. The quantum yield of elimination, measured at 254 nm by monitoring the growth of the 449-nm band of [IrCl(PPh3)3], is 0.56 0.03. 

Platinum-carbon bond cleavage can be photoinduced. The photoinduced reductive elimination of cyanoalkanes from ftwis-PtH(R)(PPh3)2 (R = CH2CN, (CH2)2CN, (CH2)3CN) involves initial isomerization to the cis isomer prior to reductive elimination.563 Photolysis of platinacyclopentanes gives alkanes and alkenes.564... 

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