Comprehensive Organometallic Chemistry III, Volume 5 : by Klaus Theopold

By Klaus Theopold

This quantity reports the training, homes, reactions and exact functions of crew 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 entire review of advancements given that 1993 and makes an attempt to foretell developments within the box over the subsequent 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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086(5) in the Hf analog. Subsequent hydrolysis gives the Zr/Hf-free acyl– vanadate complex that can be O-alkylated with [Et3O][BF4] to yield the Fischer-type (alkoxycarbene)vanadium complex. 219 Further exposure of a solution of the alkene complex to CO affords 1-butene and CpV(CO)2(PMe3)2 (Scheme 25). 1) derivatives that are described in the appropriate sections of this chapter. 1), and have only been obtained as phosphine adducts Cp9VX2(PR3)2 [Cp9 ¼ Cp, CpMe, CpEt] from the reaction of VCl3(THF)3 and Cp9M [M ¼ Tl, Na, 1/2Mg, SnBun3] in the presence of phosphine to prevent disproportionation.

133,134 One-electron oxidation of 35a and 35b with CuCl affords the vanadium(IV) d1-species V[N(SiMe3)2]2R(Cl) in moderate yield, whereas 1 equiv. of styrene oxide oxidizes 35a and 35b into oxo-vanadium(V) V(TO)R[N(SiMe3)2]2. 5 equiv. 133 Relevant structural parameters are reported in Table 7 for a comparison with other alkylvanadium(III) complexes supported by the same silylamido ligand. 134,135 In contrast, addition of 3 equiv. of benzonitrile to 35b affords the trivalent azaalkenylidene derivative 38 resulting from a monoinsertion of PhCN.

The ethylidyne fragment is unsymmetrically coordinated ˚ which indicates two non-equivalent V–C bonds (double vs. single). 10) of tetravalent and pentavalent vanadium has been examined. 163 At 423 K, neopentane adds to the VTN bond of the imido derivative via C–H addition. 164,165 It undergoes surprisingly clean thermal (58  C) -H elimination of SiMe4 to generate the supported alkylidene (USiO)2V(TCHSiMe3). When exposed to excess of styrene at room temperature, this alkylidene species affords trimethylvinylsilane by metathetical exchange.

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