Rhenium complexes spectra

Further evidence came from in situ UV-visible studies by Breikss and Abruna (1986), apparently using external reflectance from a Pt electrode. Figure 3.58(A) shows the absorption spectrum for the rhenium complex in solution in the absence of C02 prior to electrolysis. The potential of the working electrode was then slowly ramped to more cathodic values until it reached —1.7 V, whereupon a reddish material formed with a spectrum labelled B in Figure 3.58, having a Am = 512nm. The potential was then... 

Fig. 1 b shows the 2D-IR spectrum of the rhenium complex (4 mM in DMSO) in the electronic ground state. The 2D-IR spectrum is measured according to our double-resonance scheme [2,14], employing a spectrally narrow IR pump pulse and a broadband IR probe pulse... 

Analogously, the reaction of rhenate pentacarbonyl anion [Re(CO)5] as its sodium salt, with cyclopropenylium cations [C3Ph3]X (X = BF4, PF6) in THF, at -80 °C, afforded the octahedral n-coordinated pentacarbonyl ( /-l,2,3-triphenylcyclopropenyl)rhenium complex in 60-73% yield (equation 195)26 269. The l3C NMR (acetone-, .) spectrum dis-... 

Five different polymeric species containing rhenium(I) tricarbonyl complexes are shown in Fig. 17. Polymer A contained Re(CO)3Cl units attached to a dipyridyphenazine ligand [79]. The polymer components were varied from x = 0.1 and y = 0.9 to x = 1 and y = 0 with the latter variation providing the most evidence for the presence of the rhenium complex. A shoulder located at ca. 550-600 nm was attributed to the characteristic MLCT optical transition for the rhenium complex. The photoluminescence spectrum gave a continuous decrease of emission from the poly(p-phenylenevinylene) back-... 

Photolysis of Cp Mn(CO)3 in THF leads to the solvent complex Cp Mn-(CO)2(THF). Removal of solvent at -20°C followed by warming to room temperature while maintaining reduced pressure results in dimerization of solvent complex, decarbonylation, and solvent loss to form the air-sensitive 8 (17,51,88). While not isolated, the related Cp complex 8 has been observed in the gas phase. It is seen, in the electron-impact mass spectrum of the THF complex CpMn(CO)2(THF), which shows a molecular ion and cracking pattern assignable to 8 rather than the THF complex itself (51). The rhenium complex 9 is formed on photolysis of Cp Re-(CO)3 in THF (18) and in the carbonylation (15-20 atm, THF or toluene) of Cp 2Re2(0)2(ju.-0)2 (89,90). 

The prototypical photochemical system for CO2 reduction contains a photosensitizer (or photocatalyst) to capture the photon energy, an electron relay catalyst (that might be the same species as the photosensitizer) to couple the photon energy to the chemical reduction, an oxidizable species to complete the redox cycle and CO2 as the substrate. Figure 1 shows a cartoon of the photochemical CO2 reduction system. An effective photocatalyst must absorb a significant part of the solar spectrum, have a long-lived excited state and promote the activation of small molecules. Both organic dyes and transition metal complexes have been used as photocatalysts for CO2 reduction. In this chapter, CO2 reduction systems mediated by cobalt and nickel macrocycles and rhenium complexes will be discussed. 

The cationic rhenium complexes [Re(NO)2(PR3)2] (R = Cy, Pr) [50] indeed show great potential for hydrolytic activation of dihydrogen. When [Re(NO)2(PR3)2l is treated with a mixture of H2 and D2 in toluene or chlorobenzene, hydrogen-deuterium scrambling is observed, and HD can be traced in the NMR spectrum of the reaction mixture [51]. The proposed mechanism for this catalytic exchange is illustrated in Scheme 4. 

Dihalocarbene complexes are useful precursors to new carbenes by nucleophilic displacement of the chlorine substituents. This has been nicely illustrated for Fe(TPP)(=CCl2) by its reaction with two equivalents of Re(CO)5J to give the unusual /t-carbido complex Fe(TPP)=C=Re(CO)4Re(CO)5 which also contains a rhenium-rhenium bond. " The carbido carbon resonance was observed at 211.7 ppm in the C NMR spectrum. An X-ray crystal structure showed a very short Fe=C bond (1.605(13) A, shorter than comparable carbyne complexes) and a relatively long Re=C bond (1.957( 12) A) (Fig. 4, Table III). " ... 

Reaction of 3 with Ph3C+PF6" resulted in the formation of methylidene complex [(n-C5H5)Re(N0)(PPh3)(CH2)]+ PF6 (8) in 88-100% spectroscopic yields, as shown in Figure 11. Although 8 decomposes in solution slowly at -10 °C and rapidly at 25 °C (She decomposition is second order in 8), it can be isolated as an off-white powder (pure by H NMR) when the reaction is worked up at -23 °C. The methylidene H and 13C NMR chemical shifts are similar to those observed previously for carbene complexes [28]. However, the multiplicity of the H NMR spectrum indicates the two methylidene protons to be non-equivalent (Figure 11). Since no coalescence is.observed below the decomposition point of 8, a lower limit of AG >15 kcal/mol can be set for the rotational barrier about the rhenium-methylidene bond. 

A control experiment with the unfunctionalized methyl bis(3,5-dimethylpyrazol-l-yl)acetate (51) showed no occupancy of the polymer sites and subsequently no A and A" signals but a typical IR spectrum of Merrifield polymer. Therefore, the results of our experiments prove a facial coordination of rhenium(I) by the monoanionic NJ), 0 tripod ligand as well as a solid phase fixation of the ligand and the resulting tricarbonyl complex (68). 

Isolation of 3-cyclopropenyl metal compounds by this method has been achieved so far for iron and rhenium metals only. Thus, the reaction of Na[CpFe(CO)J (NaFp) with cyclopropenylium salts at -70 °C, in THF, gave 3-Fp-cyclopropene complexes (equation 194)2 267. The X-ray crystal structure of the most stable iron complex 3-Fp-C3Ph3 exhibits a regular cyclopropene C—C single and double bond distances (151 and 129 pm), and a characteristic distance of 208 pm for the Fe—C (T-bond267. The H NMR (CS2) spectrum of the 3-Fp-C3Ph,H complex displays a singlet at S = 2.63 ppm, of the cyclopropen yl proton at the 3-position. ... 

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