Download Comprehensive Organometallic Chemistry III, Volume 5 : by Klaus Theopold PDF

By Klaus Theopold

This quantity studies the guidance, homes, reactions and particular purposes of workforce five to 7 organometallic compounds. every one bankruptcy examines the compounds shaped among Vanadium, Niobium, Tantalum, Chromium, Molybdenum, Tungsten, Manganese, Technetium and Rhenium and particular ligands. It presents a transparent and complete evaluate of advancements on account that 1993 and makes an attempt to foretell tendencies within the box over the following ten years. Like its predecessors, COMC (1982) and COMC-II (1995), this new paintings is the fundamental reference textual content for any chemist or technologist who must use or practice organometallic compounds.

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Additional info for Comprehensive Organometallic Chemistry III, Volume 5 : Compounds of Groups 5 to 7

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Structure 12 can be reduced into unsolvated Cs[12] with Cs/ graphite in THF, and is oxidized by [Cp2Fe][PF6] to afford [12][PF6]. The members of this family of homoleptic isocyanides [V(CNXyl)6]z (z ¼ þ1, 0, À1) have been structurally characterized, which allows a comparison of structural and infrared data (Table 4) and clearly follow the trend of the %-accepting property of the isocyanide ligand. 78 All these compounds are high spin d 2-species, and present a characteristic #CN band listed in Table 3.

The four phenylacetylides in 18 are bridged at the -carbon between the vanadium center and two tetrahedral lithium cations. These complexes present one (for 19) or two (for 18) # CUC bands in the expected 2000 cmÀ1 region. The related V(CUCBut)2(TMEDA)2 is the only product isolated from an analogous reaction with LiCUCBut. 186 A˚ (Table 5). Reduction of vanadium occurs during these reactions, and use of vanadium(II) precursor VCl2(TMEDA)2 gives the same alkynyl complexes in higher yields. The alkynyl ligands in these complexes react with organic electrophiles at the -carbon.

Of ButNC under identical conditions takes different pathways. 131 Although no other compounds have been isolated, this complicated reaction probably results in the formation of other species. Structure 28a gives a fast reaction with the formation of the insertion product 32 in 49% yield, a vanadium(III) metallacyclic complex with a vinyl group arising, as previously shown with CO, from the insertion of the isocyanide into the Si–CH2 bond. The difference of reactivity between 26 and 28a is also apparent in the reaction with alkynes.

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