Organometallic complexes synthesis

Benzodiazepines as antianxiety agents, 1, 170 as anticonvulsants, 1, 166 organometallic complexes, 7, 604 as sedatives, 1, 166 IH- 1,2-Benzodiazepines conversion to 3H-1,2-benzodiazepines, 7, 604 synthesis, 7, 597, 598, 604 3H-1,2-Benzodiazepines acid-catalyzed reactions, 7, 601 nucleophilic reactions, 7, 604 oxidation, 7, 603 synthesis, 7, 596 thermal reactions, 7, 600 5H-1,2-Benzodiazepines photochemical reactions, 7, 599 synthesis, 7, 603... 

The Hoch-Campbell aziridine synthesis entails treatment of ketoximes with excess Grignard reagents and subsequent hydrolysis of the organometallic complex. ... 

The selective insertion of diphenylacetylene in the cyciopaiiadated sulfide complex 1 leads to the stable organometallic complex 2, which can be depalladated with silver(I) tetrafluoroborate to give a mixture of the dibenzothiepinium salt 3 and the dibenzo[Z>,z ]thiepin 4.91 Demethyla-tion of 3 to yield 4 is complete after refluxing overnight in chlorobenzene. The synthetic scope of this method for thiepin derivatives is limited due to their thermal instability, but the method is very suitable for the synthesis of 1//-2-benzothiopyrans.91... 

It is in the synthesis of organometallic complexes that the metal-atom technique shows its greatest utility. From metal vapors, many complexes may be synthesized on a macroscale that are difficult, if not impossible, to prepare by standard, wet-chemical techniques (64, 65). In this section, we shall illustrate the vast potential that the method has in this area, although, to be sure, it is evident throughout this entire review. 

The synthesis procedure consists in removing the ligands from an organometallic complex in the mildest possible conditions and with the minimum of potentially pollutant reactants. The ideal case is the reaction of an olefinic precursor with dihydrogen, which leads to the production of an alkane unable in these conditions to produce strong bonds with the growing metal surface [29]. Precursors of this type are for example Ni(CsHi2)2 [30] and... 

The synthesis of metal nanoparticles via the controlled decomposition of pre-prepared organometallic complexes or metal carbonyls where the metals are already in the zero valent or low-valent state has been known since 1970. The first examples were Pd- and Pt-dibenzylideneacetone complexes where the coordinated ligands detached using either hydrogen of carbon monoxide under mild conditions to give the respective metal nanoparticles [310]. 

Anchored organometallic complexes of tungsten were prepared by the interaction of W(C4H7)4 with surface OH groups, and the resulting surface species play a role as precursors for the synthesis of different surface tungsten compounds (Scheme 7.11).231... 

The reaction of silica-supported bis(allyl)Rh complexes with PMe3 followed by hydrogen treatment leads to the synthesis of the surface SiO-RhH2(PMe3)4+ as the first example of a cationic organometallic complex attached to the silica surface by ion pairing. The counterion is presumed to be a siloxy group SiO- on the silica surface.276 277... 

The synthesis, characterization, and catalytic properties of materials obtained by the reaction of organometallic complexes of IIB, IVA, and VIA with metallic particles were studied extensively. Two types of materials may be obtained by... 

Scheme 11). Alternatively the quaternary salts can be converted thermally into acyliron chelate complexes which can then be oxidized to azetidinones (Scheme 12). Extension of the method to the synthesis of a condensed azetidinone is illustrated in Scheme 13, but the scope of the procedure has not been evaluated. It will also be of interest to assess the utility of other cationic organometallic complexes preliminary studies have shown that molybdenum complexes behave in an analogous manner but the oxidative cyclization is inefficient (Scheme 14). 

A direct synthesis of the thiophene nucleus has been achieved by allowing air-stable cobaltacyclopentadiene complexes (66) to react with sulfur the organometallic complexes are prepared in variable yields in a stepwise fashion from f75-cyclopentadienyIbis(triphenylphosphine)cobalt (65) (Scheme 82) 147,148 Reactions of the complexes 66 with selenium and nitrosobenzene give rise to selenophenes and pyrroles, respectively. 

Silver belongs to the late transition metals and, like gold, favors coordination to C=C triple bonds. A lot of silver-containing organometallic complexes, where silver-alkyne interactions assist the assembly of the complexes, are known. None of these complexes, however, was applied to efficient carbon-carbon bond formation in organic synthesis. 

I. Ojima, A. Vu, D. Bonafoux, Organo-metallic complexes of rhodium, in Houhen-Weyl Science of Synthesis, Thieme, 2003, Chapter 1.5.3.2, p. 540 J. O Connor, Organometallic complexes of rhodium,... 

This provides new options for synthesis and purification of sensitive oiganometallic complexes N. Spetse-ris, S. Hadida, D. P. Curran, T. Y. Meyer, "Organic/fluor-ous phase extraction A new tool for the isolation of organometallic complexes , OrganometaL 1998,171458. 

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