By Christian Bruneau, Pierre Dixneuf

With concentrate on the functions in synthesis and catalysis, this publication comprehensively discusses themes starting from polymerization to metathesis, from molecular fabrics to carbon wealthy compounds together with how those compounds play the most position within the metathesis response, the 2005 Nobel Prize subject.

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Additional info for Metal Vinylidenes and Allenylidenes in Catalysis: From Reactivity to Applications in Synthesis

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Similar oxidative coupling of cyclopropenyl Ru{C¼CPhCH(CN)}(PPh3)2Cp affords bis(vinylidene) [{Cp(Ph3P)2Ru}¼C¼CPhCH(CN)2}2]2þ which, in turn, can be deprotonated to the bis(cyclopropenyl) [223]. Oxidation of [Ru(N4Me8)(¼C¼CH2)]2À with PhN3 or [FeCp2]þ affords [{Ru(N4Me8)}2(m-C¼CHCH¼C)]4À [51]. 4 From Metal Allenylidenes via Metal Alkynyls Ready addition of nucleophiles (NuÀ) to metal-allenylidene complexes affords alkynyl derivatives. 8): ½Ln M¼C¼C¼CRR0 Š þ þ Nu À ! Ln MÀC:CCðNuÞRR0 ð1:8Þ þ H !

12): ½Ln M¼C¼CHRŠ þ þ B ! Ln MÀC:CR þ ½BHŠ þ ð1:12Þ MLn is exemplified by Fe(dppm)Cp [250a], Fe(CO)(PPh3)Cp [9], Fe(dppe)Cpà [278], Ru(CO)(PMePri2)Cpà [104], trans-Ru(dppe)2 [96], Ru(dippe)Tp [127], Ru(CO)(PR3) (Z5-C9H7) [102], Ru(PMe2Ph)2Cpà [279], RuCl(PPh3)Cpà [109, 110], OsX(L)(Z6arene) [73, 74, 280]. Double deprotonation of Ru(¼C¼CH2)(PPh3)2Cp with LiBut affords the lithioalkynyl Ru(C:CLi)(PPh3)2Cp [281]. Reversal of the intramolecular reductive elimination leading to vinylidene is found on treatment of trans-IrCl(¼C¼CHR)(L)2 with CO to give IrH(CO)(C:CR)(L)2 [154].

The acid–base reactions between trans-Ir(OH)(¼C¼CR1R2)(L)2 and HC:CR3 (R3 ¼ Ph, CO2Me) give trans-Ir (C:CR3)(¼C¼CR1R2)(L)2. Migratory insertion occurs in reactions of CO with transIrR3(¼C¼CR1R2)(L)2 and with trans-IrMe(¼C¼CHPh)(L)2 to give vinyl complexes trans-Ir{(Z)-CR3¼CR1R2}(CO)(L)2 and trans-Ir{(Z)-CMe¼CHPh}(CO)(L)2, respectively, from which the corresponding alkenes could be obtained by treatment with acid. 3HF or from trans-Ir(O2CCF3)(¼C¼CHPh)(L)2 and [NBu4]F. The azido complexes trans-Ir(N3)(¼C¼CHR)(L)2 (R ¼ Ph, CO2Me), from the hydroxy compounds and NaN3, convert to trans-Ir{CH(CN)R}(CO)(L)2 under CO.

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