Copper absorption bands

On the basis of the studies described in the preceding chapters, we anticipated that chelation is a requirement for efficient Lewis-acid catalysis. This notion was confirmed by an investigation of the coordination behaviour of dienophiles 4.11 and 4.12 (Scheme 4.4). In contrast to 4.10, these compounds failed to reveal a significant shift in the UV absorption band maxima in the presence of concentrations up to one molar of copper(ir)nitrate in water. Also the rate of the reaction of these dienophiles with cyclopentadiene was not significantly increased upon addition of copper(II)nitrate or y tterbium(III)triflate. 

A number of analytical methods have been developed for the determination of chlorotoluene mixtures by gas chromatography. These are used for determinations in environments such as air near industry (62) and soil (63). Liquid crystal stationary columns are more effective in separating m- and chlorotoluene than conventional columns (64). Prepacked columns are commercially available. ZeoHtes have been examined extensively as a means to separate chlorotoluene mixtures (see Molecularsieves). For example, a Y-type 2eohte containing sodium and copper has been used to separate y -chlorotoluene from its isomers by selective absorption (65). The presence of ben2ylic impurities in chlorotoluenes is determined by standard methods for hydroly2able chlorine. Proton (66) and carbon-13 chemical shifts, characteristic in absorption bands, and principal mass spectral peaks are available along with sources of reference spectra (67). 

In the I.R. spectrum of pAANa, which is shown in Table 5, the absorption bands characteristic of the carboxylate group (- 00"), the covalent sulphate group (—O—SO2—O—), and the hydroxyl group (—OH) are due to the —COONa interaction with copper sulphate according to the following mechanisms ... 

Although this example, at face value, looks to be a case of the use of the absorption of UV/visible radiation to determine the concentration of a single ionic species (the Cu2+ ion) in solution, and, therefore, the province of the previous chapter, it is, in fact, the quantification of a molecular absorption band. In a sulfate solution, the copper ion actually exists, not as a bare ion, but as the pentaquo species, in which the central copper ion is surrounded by five water molecules and a sulfate ion in an octahedral structure (Fig. 4.1). The color of the transition metal ions arises directly from the interaction between the outer d orbital electrons of the transition metal and the electric field created by the presence of these co-ordinating molecules (called ligands). Without the aquation... 

Electronic spectra of metalloproteins find their origins in (i) internal ligand absorption bands, such as n->n electronic transitions in porphyrins (ii) transitions associated entirely with metal orbitals (d-d transitions) (iii) charge-transfer bands between the ligand and the metal, such as the S ->Fe(II) and S ->Cu(II) charge-transfer bands seen in the optical spectra of Fe-S proteins and blue copper proteins, respectively. Figure 6.3a presents the characteristic spectrum of cytochrome c, one of the electron-transport haemoproteins of the mitochondrial... 

As shown In Figure 5, azide bound to a single copper gives rise to one relatively Intense charge transfer absorption band. In analogy to peroxide, this transition originates from the level the... 

Characterization of the Type 2 Depleted Derivative of Laccase. The model for the coupled blnuclear copper site in hemocyanln and tyrosinase (Figure 7) may now be compared to the parallel site in laccase which contains a blue copper (denoted Type 1 or Tl), a normal copper (Type 2, T2), and a coupled binuclear copper (Type 3, T3) center. As shown in Figures 8a and b, native laccase has contributions from both the Tl and T2 copper centers in the EPR spectrum (the T3 cupric ions are coupled and hence EPR nondetectable as in hemocyanln), and an intense absorption band at associated with the Tl center (a thlolate —> Cu(II) CT transition).(14) The only feature in the native laccase spectra believed to be associated with the T3 center was the absorption band at 330 nm (e 3200 M cm ) which reduced with two electrons, independent of the EPR signals.(15) Initial studies have focussed on the simplified Type 2 depleted (T2D) derlvatlve(16) in which the T2 center has been reversibly removed. From Figure 8 the T2 contribution is clearly eliminated from the EPR spectrum of T2D and the Tl contribution to both the EPR and absorption spectrum remains. 

Of the important properties of glass, color is one of the most interesting. Color is usually achieved by the addition of various metal oxides. The strongest of these are titanium, vanadium, chromium, manganese, selenium, iron, cobalt, nickel and copper. Silver and uranium will give weak colors. Some of the rare earths are also used as colorants with sharp absorption bands in contrast to the broad bands given by most colorants. (4)... 

A fast and reversible copper translocation driven by the CuII/CuI couple was carried out within the flexible ditopic receptor 10.10 The translocation process, illustrated in Fig. 2.8, is fast and reversible and can be followed both visually and spectrophoto-metrically. In particular, a MeCN solution equimolar in both 10 and Cu11 is blue-violet (metal-centered absorption band = 548 nm,e = 120 M-1 cm-1), which indicates... 

The type-2 copper proteins, on the contrary, have a nearly square-planar copper environment, which is accessible to water molecules They show only weak absorption bands in the visible and normal A.. values in EPR. The main enzymatic activities are listed in Table 1. 

The spectrum of ethyne on Cu(110) at 280 K differs from those of ethyne on Ni(110) and Pd(110) at low temperatures in showing additional absorption bands and strong and well-defined vCC and vCH absorptions (56). Both of the latter bands are broad and weak for the other two metals. In the case of Fe(110), which has the different body-centered cubic (bcc) structure, the (110) plane is nearest to close-packed so that the observed type A spectrum at 120 K may have its more usual significance as indicating a four-metal-atom site not very different from that on fee (111) planes. Adsorption on Ag(110) at 100 K gives a spectrum much less strongly perturbed relative to the spectrum of the free ethyne molecule than any of the others. This clearly denotes relatively weak 77-bonding to the surface (57, 58), in marked contrast to the copper case. 

The blue color of these "type 1" copper proteins is much more intense than are the well known colors of the hydrated ion Cu(H20)42+ or of the more strongly absorbing Cu(NH3)42+. The blue color of these simple complexes arises from a transition of an electron from one d orbital to another within the copper atom. The absorption is somewhat more intense in copper peptide chelates of the type shown in Eq. 6-85. However, the -600 nm absorption bands of the blue proteins are an order of magnitude more intense, as is illustrated by the absorption spectrum of azurin (Fig. 23-8). The intense blue is thought to arise as a result of transfer of electronic charge from the cysteine thiolate to the Cu2+ ion.520 521... 

Gaussian curves (normal distribution functions) can sometimes be used to describe the shape of the overall envelope of the many vibrationally induced subbands that make up one electronic absorption band, e.g., for the absorption spectrum of the copper-containing blue protein of Pseudomonas (Fig. 23-8) Gaussian bands are appropriate. They permit resolution of the spectrum into components representing individual electronic transitions. Each transition is described by a peak position, height (molar extinction coefficient), and width (as measured at the halfheight, in cm-1). However, most absorption bands of organic compounds are not symmetric but are skewed... 

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