Oxophilic species

The final category of extractants, considered in this chapter, isthemacrocyclic/macromolecular group. These are frequently based on large crown ether moieties and are particularly useful in extracting oxophilic species. Macrocycles can often be tailored to a specific application and they have been applied to the separation of a wide number of metallic species, although not extensively for the PIM separation of U to date (Nghiem et al., 2006). 

Ketyl radicals are also available using tributylstannyl radicals as oxophilic species. O-tributylstannyl ketyls are produced under neutral radical conditions by reaction of the carbonyl group with TBTH and AIBN (142 143). The overall process (142—>146, Scheme 25.68) leads to compound 146, which is formed by a cascade process involving the ring opening of cyclopropylmethyl radical 143, cyclization of the resulting 144, and protonation of enolate 145 after its radical reduction. 

The only reports of directed synthesis of coordination complexes in ionic liquids are from oxo-exchange chemistry. Exposure of chloroaluminate ionic liquids to water results in the formation of a variety of aluminium oxo- and hydroxo-contain-ing species [4]. Dissolution of metals more oxophilic than aluminium will generate metal oxohalide species. FFussey et al. have used phosgene (COCI2) to deoxochlori-nate [NbOa5] - (Scheme 6.1-1) [5]. 

These limitations were overcome with the introduction of the well-defined, single-component tungsten and molybdenum (14) alkylidenes in 1990. (Fig. 8.4).7 Schrock s discoveiy revolutionized the metathesis field and vastly increased die utility of this reaction. The Schrock alkylidenes are particularly reactive species, have no side reactions, and are quite effective as polymerization catalysts for both ROMP and ADMET. Due to the oxophilicity of molybdenum, these alkylidenes are moisture and air sensitive, so all reactions using these catalysts must be performed under anaerobic conditions, requiring Schlenk and/or glovebox techniques. 

The catalytic process is also achieved in the Pd(0)/Cr(II)-mediated coupling of organic halides with aldehydes (Scheme 33) [74], Oxidative addition of a vinyl or aryl halide to a Pd(0) species, followed by transmetallation with a chromium salt and subsequent addition of the resulting organo chromate to an aldehyde, leads to the alcohol 54. The presence of an oxophile [Li(I) salts or MesSiCl] allows the cleavage of the Cr(III) - 0 bond to liberate Cr(III), which is reduced to active Cr(II) on the electrode surface. 

In contrast, Fe-Hg-X complexes show little tendency to form halide bridged species and less is known about complexes containing Zn. We first reported the formation of Fe-Si-O-M four membered ring systems with soft metals M = Ag, Rh, Pd, and Pt, and then prepared bimetallic complexes with more oxophilic metals in order to better understand the conditions for the occurrence of this unusual (t-alkoxy-silyl bridging mode. We have expanded our studies on Cd-containing complexes [3b-d] to Group 13 elements and we report here about the synthesis and reactivity of new, stable heterometallic Fe-M (M =... 

Rhenium is one of the oxophilic atoms effective for oxidation reactions. ReOx species are likely to have chemical interaction with various oxide supports and exhibit unique catalytic properties that cannot be observed on monomeric rhenium oxides. A new active six-membered octahedral Re cluster in zeolite pores (H-ZSM-5 [HZ]) is produced from inactive [Re04] monomers in situ under selective propene oxidation to acrolein (C3H6+02 - CH2=CHCH0+H20) in the presence of ammonia that is not involved in the reaction equation [16], The cluster is transformed back to the original inactive monomer in the absence ammonia. Note that coexistence of spectator NH3 is indispensable for the selective oxidation. 

Pt alloy monolayer catalysts exhibited even more active ORR behavior compared to Pt monolayer catalysts. To understand this phenomenon computational DFT studies were carried out. The hypothesis to be tested was that, for instance, Ru metal atoms in the Pt—Ru monolayer are OH-covered and could inhibit the adsorption of additional OH on neighboring surface sites (adsorbate-adsorbate repulsion effect). A very similar hypothesis was put forward about three years earlier by Paulus et al. [105] who postulated that Co surface atoms might exhibit a so-called common-ion effect, that is, they could repel like species from neighboring sites. A combined computational-experimental study finally confirmed this hypothesis [123] If oxophilic atoms such as Ru or Os were incorporated into the Pt monolayer catalysts, the formation of adjacent surface OH was delayed, if not inhibited. Oxo-phobic atoms, such as Au, displayed the opposite effect, would not inhibit Pt—OH formation, and were found to be detrimental to the overall ORR activity. 

The detailed mechanism for the formation of reduced Cu+ species under the hydrothermal synthesis conditions in the presence of CTAB without any additional reducing reagent is not clear at present, but the degree of reduction of the Cu- and oxide-precursors may depend on the oxophilicity of metal oxides Cu oxide (most reducible) < Mo oxide < Zn oxide < Si oxide < A1 oxide Zr oxide Ce oxide (hard to reduce). Further, chemical interaction of the Cu + clusters with the Ce02 surface may also be the key to stabilizing the Cu + clusters on the support. 

In fact, P3RhCl has been shown to produce more than 3 mol of carbonate per Rh, thus demonstrating that the Rh(C03) species can indeed act as a catalyst. Moreover, an oxophile such as a phosphane ligand can extract an O-atom from the coordinated carbonate (Equation 7.17c), thus regenerating Rh(I) and... 

The starting material bis(pinacolato)diboron is a poor Lewis acid and 1 B-NMR of KOAc and B2bin2 in DMSO-d6 shows no evidence of the coordination of the acetoxy anion to a boron atom leading to a tetrahedral activated species. However, the formation of an (acetato)palladium(II) complex after the oxidative addition of the halide influences the reaction rate of the transmetalation step. The Pd-O bond, which consists of a hard Lewis base with a soft Lewis acid, is more reactive than a Pd-X (X=Br, I) bond. In addition, the high oxophilicity of boron has to be considered as a driving force for the transmetalation step, which involves an acetato ligand. 

This simple example may illustrate that in general the reaction of an organic halide salt [cation]X with an excess of a Lewis-acid MXy can result in new catalytic materials even if other Lewis-acids are applied than AICI3. In contrast, the use of other Lewis-acids to form the ionic liquid of type [cation][MXy+i] + excess MXy (the excess of MXy may be dissolved in the neutral ionic liquid or may form acidic anionic species such as e.g. [M2X2y+i]-) gives access to new combinations of properties (e.g. a liquid, less oxophilic, Lewis-acidic catalyst with defined solubility and acidity properties). In Table 2 other examples of ionic liquids are presented which are formed by the reaction of an organic halide salt with different Lewis-acids. All these systems should be in principle useful acidic catalysts for synthetic organic chemistry even if not all displayed examples have been already discribed in the literature for this application. 

In the Au(I) catalysis of electron-poor alkynes such as 4, the catalytically active species is likely to be a cationic ligand-stabilized gold(I) Jt-complex, as in previously reported additions of oxygen nucleophiles to alkynes [5], Gold catalysts are very soft and thus carbophilic rather than oxophilic. On the basis of this assumption a plausible mechanism can be formulated as shown in Scheme 6. The cationic or strongly polarized neutral Au(I)-catalyst coordinates to the alkyne, and nucleophilic attack of the electron-rich arene from the opposite side leads to the formation of a vinyl-gold intermediate 7 which is stereospecifically protonated with final formation of the Z-olefm 8 [2, 4]. Regioselectivity is dominated by elec-... 

In fact, only in some cases are real carbenoid species involved in these reactions. The reactions employing oxophilic metals such as Zn, Fe, Sm, and In were reported [9], and representative examples are given in Scheme 3. Such reactions exhibit obvious synthetic limitations, since only aromatic (unsaturated) carbonyl compounds can be used, and/or cyclopropanes of a very specific structure obtained. The Kulinkovich and related reactions, involving dianion equivalents (1, Scheme 1), represent the only synthetically useful deoxygenative process at present. 

Titanium. The high reducing ability and the pronounced oxophilicity of early transition metals in low oxidation states act jointly as a formidable driving force in many transformations. However, such processes are usually hampered by the fact that the metal oxides or alkoxides formed as the inorganic by-products usually resist attempted re-reductions to the active species and thus render catalysis a difficult task. 

In early proposals based upon the mechanisms of Mo and V peroxides, Ti(T] —O2) was thought to be the active species [70, 71]. The epoxidation of the olefin occurred either by a coordinative mechanism, with the olefin adsorbing on Ti prior to the insertion into one Ti-peroxide bond, or by the attack of one peroxy oxygen directly on the double bond. However, the chemical inertness of known Ti(T] —O2) peroxides, the unhkelihood of olefin adsorption on oxophilic Ti in competition with the protic medium and other evidence led subsequently to the loss... 

An example of fortuitous vanadium enolate chemistry is the CO addition reaction to a silylamido vanadium species in which the dimeric metallocycle 32 is transformed into the corresponding cyclic enolate 33, as shown in equation 12. Given silicon s profound oxophilicity, the absence of the Si-O moieties in 33 is surprising. For example, the liquid phase reaction shown in equation 13 is exothermic by ca 420 kJmol , as determined from the enthalpies of formation of tetramethoxymethane and the silicon compounds . 

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