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Metal carbonyls carbene complexes

In situation (a) a strong carbon-metal bond results. To this group belong the typical Schrock-type carbenes [e.g. Np3Ta=CH(7Bu)], many of which are nucleophilic at carbon. Situation (b) should also lead to nucleophilic carbene complexes, albeit with a weaker carbon-metal bond. Typical reactions of nucleophilic carbene complexes include carbonyl olefination (Section 3.2.4) and olefin metathesis (Section 3.2.5). [Pg.2]

Transition metal complexes which react with diazoalkanes to yield carbene complexes can be catalysts for diazodecomposition (see Section 4.1). In addition to the requirements mentioned above (free coordination site, electrophi-licity), transition metal complexes can catalyze the decomposition of diazoalkanes if the corresponding carbene complexes are capable of transferring the carbene fragment to a substrate with simultaneous regeneration of the original complex. Metal carbonyls of chromium, iron, cobalt, nickel, molybdenum, and tungsten all catalyze the decomposition of diazomethane [493]. Other related catalysts are (CO)5W=C(OMe)Ph [509], [Cp(CO)2Fe(THF)][BF4] [510,511], and (CO)5Cr(COD) [52,512]. These compounds are sufficiently electrophilic to catalyze the decomposition of weakly nucleophilic, acceptor-substituted diazoalkanes. [Pg.91]

Carbon-13 NMR parameters for all metal carbonyl complexes discussed in this section appear in Table XL. Additional carbonyl data for carbene substituted metal carbonyl complexes may be found in Tables XXXVI and XXXVII. Notably absent from this section is a discussion of polynuclear metal carbonyl complexes. These studies are considered in the section of fiuxional complexes. It is sufScient to note at this point that bridging carbonyl ligands always appear at lower fields than terminal carbonyl ligands. [Pg.353]

The mechanisms of these reactions bear marked similarities, in spite of the differences in their reactivities and selectivities. Thus, in certain cases, a four-membered intermediate similar to the 1,2-oxaphosphetane intermediate in the Wittig reaction appears in the Peterson reaction as a pentacoordinate 1,2-oxasiletanide. Reactions of transition metal carbene complexes with carbonyl compounds also proceed through the formation of a four-membered oxametallacycle, which was recently found to be an intermediate of some McMurry reactions. Carbonyl olefination utilizing dimetallic species of zinc or chromium is somewhat similar to the Julia reaction in that they both involve the process of ) -elimination. [Pg.364]

It is assumed that compound (37) is produced by an analogous mechanism to that postulated for the synthesis of Fischer carbenes from metal-carbonyl or metal-isonitrile complexes according to Scheme 2.20. [Pg.38]

Many other organometaUic compounds also react with carbonyl groups. Lithium alkyls and aryls add to the ester carbonyl group to give either an alcohol or an olefin. Lithium dimethyl cuprate has been used to prepare ketones from esters (41). Tebbe s reagent, Cp2TiCH2AlCl(CH2)2, where Cp = clyclopentadienyl, and other metal carbene complexes can convert the C=0 of esters to C=CR2 (42,43). [Pg.389]

The 13C-NMR spectra of 4-7, 9-11 show a close similarity to the spectral data of analogous carbene complexes. The shift differences between the metal carbonyls of the silylene complexes and the related carbon compounds are only small. These results underline the close analogy between the silicon compounds 4-7, 9-11 and Fischer carbene complexes. This view is also supported by the IR spectral data. On the basis of an analysis of the force constants of the vco stretching vibration,... [Pg.18]

These carbene (or alkylidene) complexes are used for various transformations. Known reactions of these complexes are (a) alkene metathesis, (b) alkene cyclopropanation, (c) carbonyl alkenation, (d) insertion into C-H, N-H and O-H bonds, (e) ylide formation and (f) dimerization. The reactivity of these complexes can be tuned by varying the metal, oxidation state or ligands. Nowadays carbene complexes with cumulated double bonds have also been synthesized and investigated [45-49] as well as carbene cluster compounds, which will not be discussed here [50]. [Pg.6]

AT-heterocyclic carbenes show a pure donor nature. Comparing them to other monodentate ligands such as phosphines and amines on several metal-carbonyl complexes showed the significantly increased donor capacity relative to phosphines, even to trialkylphosphines, while the 7r-acceptor capability of the NHCs is in the order of those of nitriles and pyridine [29]. This was used to synthesize the metathesis catalysts discussed in the next section. Experimental evidence comes from the fact that it has been shown for several metals that an exchange of phosphines versus NHCs proceeds rapidly and without the need of an excess quantity of the NHC. X-ray structures of the NHC complexes show exceptionally long metal-carbon bonds indicating a different type of bond compared to the Schrock-type carbene double bond. As a result, the reactivity of these NHC complexes is also unique. They are relatively resistant towards an attack by nucleophiles and electrophiles at the divalent carbon atom. [Pg.12]

Charge. The small amount of charge distribution data for carbyne complexes (based on Mulliken population analyses) indicates that the metal-carbon bond is generally polarized Ms+—C5- and that the carbyne carbon is always more negative than adjacent carbonyl carbons (28,30). These conclusions are directly analogous to those derived for carbene complexes. [Pg.131]

Fischer carbenes characteristically contain a number of electron-withdrawing carbonyl ligands while the typical Ru, Os, or Ir carbene complexes described above frequently contain several cr-donor ligands. The metal centers in these former compounds, then, are rather electron-deficient, with nucleophilic attack at Ca being a favorable reaction. [Pg.153]

Cycloaddition of the carbene chromium complexes 97 with CO incorporation provides a versatile method for naphthol synthesis, in which the metallacy-clic intermediates 99 are involved [47]. An alternative entry to 101 is achieved by metal carbonyl-catalyzed rearrangement of the cyclopropenes 98 via the same metalla-cyclobutenes 99 and vinylketene complexes 100 [52], Mo(CO)6 shows a higher activity than Cr(CO)6 and W(CO)6. The vinylketene complex 103 is formed by the regioselective ring cleavage of 1,3,3-trimethylcyelopropene 102 with an excess of Fe2(CO)9 [53]. (Scheme 35 and 36)... [Pg.122]

Alkenyl Fischer carbene complexes can serve as three-carbon components in the [6 + 3]-reactions of vinylchro-mium carbenes and fulvenes (Equations (23)—(25)), providing rapid access to indanone and indene structures.132 This reaction tolerates substitution of the fulvene, but the carbene complex requires extended conjugation to a carbonyl or aromatic ring. This reaction is proposed to be initiated by 1,2-addition of the electron-rich fulvene to the chromium carbene followed by a 1,2-shift of the chromium with simultaneous ring closure. Reductive elimination of the chromium metal and elimination/isomerization gives the products (Scheme 41). [Pg.625]

Metal bromides, 4 322-330 Metal can food packaging, 18 37-39 Metal-carbene complexes, 26 926 Metal-carbon compounds, 4 648, 650 Metal-carbon eutectic fixed points, 24 454 Metal carbonyl catalysts, supported, 16 75 Metal carbonyl complexes, 16 73 Metal carbonyls, 15 570 16 58-78 bonding and structure of, 16 59-64 from carbon monoxide, 5 12 in catalysis, 16 72-75 economic aspects of, 16 71 health and safety aspects of, 16 71 heteronuclear, 16 69-71 high nuclearity, 16 66-69 high nuclearity carbonyl clusters, 16 64-66... [Pg.565]

Reaction of (butadiene)ZrCp2 (31/32), and substituted Cp variants, with a wide range of metal-carbonyl complexes, generates the chelated metal-carbene complexes 163 (equation 22)163. The crystal structure of a number of these complexes has been determined... [Pg.942]

Because of n-electron donation by the heteroatom, these carbene complexes are generally less electrophilic at C than the corresponding non-heteroatom-substituted complexes (Chapter 3). This effect is even more pronounced in bis-heteroatom-substituted carbenes, which are very weak Tt-acceptors and towards low-valent transition metals show binding properties similar to those of phosphines or pyridine. Alkoxycarbenes, on the other hand, have electronic properties similar to those of carbon monoxide, and stable heteroatom-monosubstituted carbene complexes are also usually formed from metals which form stable carbonyl complexes. [Pg.13]

As discussed in previous sections, high-valent carbene complexes of early transition metals have ylide-like, nucleophilic character. Some Schrock-type carbene complexes react with carbonyl compounds in the same manner as do phosphorus ylides, namely by converting the carbonyl group into an alkene. [Pg.125]

A series of reagents have been developed which are prepared in situ from a geminal dihalide or a dithioacetal [635,730] and a transition metal complex. Titanium-based reagents of this type olefinate a broad range of carbonyl compounds, including carboxylic acid derivatives (Table 3.12), and are a practical alternative to the use of isolated carbene complexes. [Pg.129]

The increased stability of ruthenium carbene complexes towards oxygen-containing compounds might be because later transition metals, having more d-electrons, are softer and hence react better with soft bases, e.g. olefins. The early transition metals, on the other hand, having few d-electrons, are generally harder and react preferentially with hard bases, such as water or carbonyl compounds. [Pg.144]

Recently, the oxidative addition of C2-S bond to Pd has been described. Methyl levamisolium triflate reacts with [Pd(dba)2] to give the cationic palladium complex 35 bearing a chiral bidentate imidazolidin-2-ylidene ligand [120]. The oxidative addition of the levamisolium cation to triruthenium or triosmium carbonyl compounds proceeds also readily to yield the carbene complexes [121], The oxidative addition of imidazolium salts is not limited to or d transition metals but has also been observed in main group chemistry. The reaction of a 1,3-dimesitylimidazolium salt with an anionic gallium(I) heterocycle proceeds under formation of the gaUium(III) hydrido complex 36 (Fig. 12) [122]. [Pg.108]

In traditional synthetic organic chemistry, the Wittig reaction plays an important role in carbon-carbon bond extension from the carbonyl group. CM is an attractive alternative for carbon-carbon extension from a terminal alkene. In fact, a pyrroh-dine ring of anthramycin derivative 55 has been constructed by RCM of 52, and the sidechain has been extended by CM of terminal alkene of 54 with ethyl acrylate. " In the CM, ruthenium carbene complex Ij, reported by Blechert, gives a good result since the ligand of the catalyst easily dissociated from the ruthenium metal at room temperature ... [Pg.167]


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