Noble metal carbonyl derivatives

Thallium(i) salts have long been used in reactions with organic and organometallic halide complexes as a means of activating the halide by removal as insoluble T1X. However, the thallium ions proved not to be innocent bystanders, and numerous examples were reported in COMC (1995) where the metal-bound thallium complexes were formed. Deliberate reactions of thallium(i) and thallium(m) salts with metal carbonyl anions have yielded a variety of complexes of the form T1 MLJ3. In the past decade, new examples of metal carbonyl derivatives of thallium have been prepared (see Table 2). In addition, the propensity for Tl+ to form adducts with 16-electron noble metal complexes has been exploited. 

The most important esters in connection with Li batteries are y-butyrolactone (BL) and methyl formate (MF). Li is apparently stable in both solvents due to passivation. Electrolysis of BL on noble metal electrodes produces a cyclic 0-keto ester anion which is a product of a nucleophilic reaction between a y-butyrolactone anion (produced by deprotonation in position a to the carbonyl) and another y-BL molecule. FTIR spectra measured from Li electrodes stored in y-BL indicate the formation of two major surface species the Li butyrate and the dilithium cyclic P-keto ester dianion. The identification of these products and related experimental work is described in detail in Refs. 150 and 189. Scheme 3 shows the reduction patterns of y-BL on lithium surfaces (also see product distribution in Table 3). In the presence of water, the LiOH formed on the Li surfaces due to H20 reduction attacks the y-BL nucleophilically to form derivatives of y-hydroxy butyrate as the major surface species [18] [e.g., LiO(CH2COOLi)]. We have evidence that y-BL may be nucleophilically attacked by surface Li20, thus forming LiO(CH2)3COOLi, which substitutes for part of the surface Li oxide [18]. MF is reduced on Li surfaces to form Li formate as the major surface species [4], LiOCH3, which is also an expected reduction product of MF on Li, was not detected as a major component in the surface films formed on Li surfaces in MF solutions [4], The reduction paths of MF on Li and their product analysis are presented in Scheme 3 and Table 3. 

Alkene hydrogenation, alkane hydrogenolysis, and methanation of CO are used as test reactions for evaluating the catalytic activity of cluster-derived metal catalysts. Catalysts derived from noble metal carbonyl precursors such... 

A further development of the Reppe acrylic acid synthesis is the reaction, described in recent literature, of the noble metal-catalyzed carbonylation of higher acetylenes to give the corresponding acrylic acid derivatives. Thus, for example, the Pd-catalyzed carbonylation of propyne (eq. (10)) in the presence of methanol leads directly to methyl methacrylate [23]. Based on this work. Shell has developed a new production process for methyl methacrylate [24]. The propyne required can be isolated from the product streams from crackers, (cf. Section 2.3.2.3). 

Hvdro en tion of Ethylene. This test reaction has been ran under a variety of activation conditions. Catalysts derived from Cr(CO)g, Mo(CO)g, W(CO)6, Ru3(CO).2. Os (CO)l2. and the Fe carbonyls have been found to be at least 10-fold more active than their traditional counterparts. The dichotomy between the more difficult to reduce metals and those easier to reduce is beautifully exemplified by the data in Tables IV and V. It is seen that catalysts derived from the more difficult to reduce metals show better activity after activation in the 0 region, whereas catalysts derived from more noble metals are more active after a high temperature reduction. It might also be noted that these catalysts are orders of magnitude more active than immobilized carbonyl complexes (16). 

Since the late 1990s, new approaches to the dispersion of noble metal particles in polymer matrixes by means of chemical, photochemical and radiation-chemical reduction, the evaporation of metal atoms (including solvated ones) into different supports, etc. have been developed (see Section 8-1) [44]. Nevertheless, catalysts prepared from individual immobilized metal clusters have more definite, mostly predetermined, structures. For these purposes derivatives of Oss, It4, RU4, Rh4, Rh6, etc. clusters are most often used. Earlier studies [46] showed that the rate of ethylene hydrogenation promoted by tetrairidium or tetraruthenium carbonyl clusters bound to phosphynated polymers decreased with an increase of the number of donor... 

Nickel is the only metal to react directly with carbon monoxide at room temperature at an appreciable rate, although iron does so on heating under pressure. Cobalt affords HCo(CO)4 with a mixture of hydrogen and carbon monoxide (p. 387). In general, therefore, direct reaction does not provide a route to metal carbonyls. The metal atom technique (p. 313) has been used to prepare carbonyls of other metals in the laboratory e.g. Cr(CO)g, but it offers no advantages over the reduction method discussed below. When metal vapours are cocondensed with carbon monoxide in frozen noble gas matrices at very low temperatures (4-20K) the formation of carbonyl complexes is observed. These include compounds of metals which do not form any stable isolable derivatives e.g. Ti(CO), Nb(CO) and Ta(CO)g as well as Pd(C0)4 and Pt(C0)4. Vibrational spectra of the matrix show that coordinatively unsaturated species such as Ni(CO) n = 1-3) or Cr(CO) (n = 3-5) are also formed under these conditions. 

Noble-Metal Carbonyl Derivatives. While many of the results discussed here are very recent, the beginnings go back well into the last century. The synthesis of plati-num(II)carbonyl chlorides was reported by Schiitzenberger in 1870 (61-63). This predates the discovery of Ni(CO)4 and marks the start of transition-metal carbonyl chemistry. Likewise, the first synthesis of gold(I)carbonyl chloride, Au(CO)Cl, by Manchot and Gall (64) and its independent synthesis by Kharash and Isbell (65) date back into the first half of this century. 

It has become apparent from the observation of vCO above 2200 cm l and from stretching force constants above 20 x 10 Nm"l for [Au(CO)2] " and [Pt(CO)4]2" ", diat these binary carbonyl cations differ drastically from classical transition-metal carbonyls with terminal CO groups, where vCO is foxmd in the general range of 2125 to 1850 cm (79, 80) and force constants usually between 15 and 1710 Nm l. It is obvious that Tc-backdonation, which is essential in transition-metal carbonyls (81), must be absent or substantially reduced and that carbon monoxide does not function as a 71-acceptor, but rather as a a-donor in noble-metal carbonyl cations and their cationic derivatives. It is not surprising that other distinguishing features, descriptive or experimental in nature, differ as well for both groups. 

On the descriptive side, previously known binary carbonyl cations are usually of the [M(C0)6] type with M = Mn, Tc or Re (82), The oxidation state of the metal in these or other ternary cations is 0 or +1, and the ionic charge of the complex does not exceed +1. In addition, far more basic anions are used as counter ions. The effective atomic number rule, which plays an important role in judging stability, structure and reactivity of transition-metal carbonyls, is not valid for the noble-metal carbonyl compounds reported so far. The silver(I) and gold(I) carbonyl derivatives have 14, and the Pt(II) carbonyls have 16 electrons in the metal valence shell. 

Hence it is more appropriate to view noble-metal carbonyls and their derivatives as coordination complexes of CO rather than as organometallic compounds. A comparison to metal cyanide complexes is far more appropriate, in particular since [Au(CO)2]+ and [Au(CN)2] as well as [Pt(CO)4]2+ and [Pt(CN)4]2- are isoelec-tronic and isostructural pairs. Strong bonding similarities have been established for the first pair (9). It is unlikely that cationic metal-carbonyl complexes will ever form so many different species as the cyanide complexes, which are known for most transition metals (86). With useful and facile synthetic routes available, further examples of cationic metal carbonyls with similar bonding and spectroscopic features as described here should be prepared and characterised in the future. 

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