Complex with carbonyl

To this category belong, e.g., homogeneous photocatalytic systems based on soluble metal complexes or organic dyes as photocatalysts. Instructive examples are photoreactions assisted by heteropolyacids (HPAs), transition meal complexes with carbonyl, phosphine or some other ligands, and metal porphyrins. 

Cavell KJ, McGuinness DS (2007) Palladium complexes with carbonyl, isocyanide and carbene ligands. In Crabtree RH, Mingos DMP, Canty AJ (eds) Comprehensive organometallic chemistry 111. Elsevier, Amsterdam... 

Dixon, K. R. Dixon, A. C. Palladium Complexes with Carbonyl, Isocyanide and Carbene Ligands, In Comprehensive Organometallic Chemistry II A review of the literature 1982-1994 Puddephatt, R. J. Ed., Elsevier, 1995, Vol. 9, p 193. 

Platinum(II) Complexes with Carbonyl and Silicon-donor Ligands 688... 

A number of complexes with carbonyl and hydride bridges have been discussed above and phosphido bridges are discussed below. The most common of the other bridges are sulfur and... 

Jiang S, Agoston GE, Chen T, Cabal M-P, Turns E (1995) BF3 Et20-promoted allylation reactions of allyl(cyclopentadienyl)iron(II) dicarbonyl complexes with carbonyl compounds. Organometallics 14 4697 -709... 

The earliest examples were provided by the work of Stone et al. on reactions of zero-valent Pt complexes with carbonyls of the iron triad (10,36,37). Thus... 

A number of molecular mechanics studies of metal-cyclopentadienyl complexes have been reported recently. The systems studied include linear metallocenes (in particular ferrocene), ferrocene derivatives (such as complexes with substituted cy-clopentadienyl ligands, bis(fulvalene)diiron complexes, ferrocenophanes and mixed-ligand complexes with carbonyls and phosphines), and nonlinear cyclopentadienyl complexes 8,153,221 231]. 

Metal-chromium phosphido-bridged complexes, with carbonyls, 5, 217... 

Reactions with fluoride ion With the exception of CF3OH (see the next section), fluorinated alcohols of the type RpCF20H are not known [124] but complexes of K, Rb, Cs, Ag or (C2H5)4N+ fluorides with hexafluoroacetone have been isolated [125, 126], following from the earlier isolation of some similar complexes with carbonyl fluoride [127]. These complexes have been reasonably formulated as fluorinated alkox-ides (Figure 8.27), but the use of these salts in synthesis is often difficult because the complexes may also act as fluoride-ion donors [128]. 

Methyl-3,5-diphenyl-l//-thiopyran 1-oxide forms red air-stable complexes with carbonyls of chromium, molybdenum and tungsten. (78CB1709). X-Ray diffraction measurements on these compounds confirm the non-planarity of the thiabenzene oxide nucleus and reinforce the evidence for high inversion barriers at sulfur. These complexes are found in isomeric forms with either the sulfur-oxygen bond axial to the half-chair conformation adopted by the ring, or the S- methyl group axial the complexes cannot be interconverted. 

Organoaluminum compounds are highly oxygenophilic, and hence are capable of forming long-lived monomeric 1 1 complexes with carbonyl substrates. For example, the reaction of benzophenone with McsAl in 1 1 molar ratio gives a yellow, long-lived monomeric 1 1 species which decomposes unimolecularly to dimethylaluminum 1,1-diphenylethoxide after some minutes at 80 °C or many hours at 25 °C [124]. 

In contrast to boron-centered Lewis acids, tin and titanium derivatives prefer a 1 2 (acidibase) stoichiometry in complexation with carbonyls. and H NMR spectra of an equimolar solution of SnCU and 4-r-butylbenzaldehyde showed sign s only for free ligand and a 1 2 (acid base) complex over a wide temperature range. Only with excesses of SnCU was any 1 1 adduct observed and even in the presence of 10 equiv. of Lewis acid, only 25% of the 1 1 complex could be detected. Intermolecular exchange in this case was shown to be slow below -40 "C and no syn-anti isomerization could be detected. 

The reaction of metal carbonyl complexes with carbonyl anions is a widely used technique for synthesis of mixed-metal clusters. This reaction is also termed reductive condensation or redox condensation. The metal carbonyl anion may be generated in situ or may be separately isolated. The mixed-metal product is usually an anion protonation can be used to generate a neutral cluster hydride. 

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